EDXRF as an analytical tool in art: Case studies from pigment identification and treatment assessment

Energy dispersive X-ray fluorescence (EDXRF) was employed for the identification of pigments decorating Hellenistic figurines, and the assessment of the efficiency of a treatment with barium hydroxide applied to stone. Elements present in the colored areas of the figurines, as well as the treated stone was identified by EDXRF. These data together with complementary information obtained by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD) led to the identification of several precious pigments. As far as the treatment efficiency is concerned, EDXRF analysis revealed that barium is unevenly distributed on the treated surface and reaches a maximum depth of 2.5 mm.     

Elemental composition and microstructure analysis of a rabbit urolith

Following physical examination and radiography analysis, cystotomy was performed to remove a rabbit’s single bladder stone. This rabbit urolith was analyzed by X-ray fluorescence spectrometry (EDXRF) and scanning electron microscopy (SEM). The EDXRF technique was successful for the determination of major elements (Ca, Mg, P, K and S) and presented sufficient sensitivity to also trace elements (Sr, Fe, Cu, V, Cr, Mn, Zn and Pb) determination. The results showed significant quantitative and structural variations among the urolith regions. The EDXRF technique using the fundamental parameters method and SEM attend as complementary techniques that can be useful in the management of urinary stone analysis.     

Studies of kidney stones using INAA,EDXRF and XRD techniques

Four kidney stones collected from patients being treated in the Advance Urology Centre of PGIMR, Chandigarh were characterized using instrumental neutron activation analysis (INAA), energy dispersive X-ray fluorescence (EDXRF) and X-ray diffraction (XRD) techniques. For INAA, samples were irradiated in tray rod facility of Dhruva reactor, Mumbai and pneumatic fast transfer system of KAMINI reactor, IGCAR, Kalpakkam. Radioactive assay was carried out using HPGe detector coupled to 8k channel analyzer. Elements determined in the samples by INAA are Zn, Sr, Co, Fe, Cr, Sc, Se, Na and Mn. EDXRF was used for the quantification of Ca. XRD patterns showed that three of the kidney stones are calcium oxalate stone and the other one is uric acid stone. The concentrations of trace elements in general were found to be higher in calcium oxalate stones and positive correlation was observed in the concentrations of Ca with Sr and Zn.     

Trace element study of kidney stones from subjects belonging to stone belt region of India

Kidney stones obtained from six patients belonging to the stone belt region of India (Punjab) were analyzed for inorganic constituents using instrumental neutron activation analysis (INAA) and energy dispersive X-ray fluorescence (EDXRF) techniques. For INAA, samples were irradiated along with IAEA RM Soil 7 as reference standard in CIRUS reactor, BARC, Mumbai. Gamma activity of irradiated samples was measured using a 45% relative efficiency HPGe detector coupled to 8?k channel analyzer. EDXRF method was used for determination of concentration of Ca. The concentrations of ten elements namely Ca, Na, K, Mn, Co, Cr, Zn, Br, Sm and Cl, are reported and discussed.     

Evaluation of barium hydroxide treatment efficacy on a dolomitic marble

The Arch of Peace, by Luigi Cagnola, is one of the most famous neoclassical monuments in Milan. It has been subjected to conservative intervention in 1998. In the present paper the efficacy of the consolidation by means of barium hydroxide has been evaluated. The stone material showed severe degradation phenomena as: erosion, pulverisation, exfoliation. The analytical data acquired through X-ray diffraction (XRD), infrared spectrophotometry (FTIR) and scanning electron microscopy (SEM-EDX), allowed to compare the conditions of stone before and after the treatment with barium hydroxide. The presence of barium has been put in evidence mainly on the surface as barium sulphate, whereas barium is only sporadically present within the thickness of the decayed material. The treatment was judged not satisfying and its inefficacy is, most probably, due to a not suitable cleaning procedure carried out before the consolidation.     

Characterization of Japanese color sticks by energy dispersive X-ray fluorescence,X-ray diffraction and Fourier transform infrared analysis

This work comprises the use of energy dispersive X-ray fluorescence (EDXRF), X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) techniques for the study of the composition of twentieth century traditional Japanese color sticks. By using the combination of analytical techniques it was possible to obtain information on inorganic and organic pigments, binders and fillers present in the sticks. The colorant materials identified in the sticks were zinc and titanium white, chrome yellow, yellow and red ochre, vermillion, alizarin, indigo, Prussian and synthetic ultramarine blue. The results also showed that calcite and barite were used as inorganic mineral fillers while Arabic gum was the medium used. EDXRF offered great potential for such investigations since it allowed the identification of the elements present in the sample preserving its integrity. However, this information alone was not enough to clearly identify some of the materials in study and therefore it was necessary to use XRD and FTIR techniques.     

唐代彩绘陶俑中无机颜料的化学组成

采用X射线粉末衍射（XRD）、X射线荧光光谱（XRF）和扫描电子显微镜-能谱（SEM-EDS）等测试技术对西安西曹M16唐墓出土的2尊唐代彩绘陶俑颜料进行了化学组成分析。结果表明,陶俑中含有丰富的无机颜料,其中红色颜料的显色成分为铅丹（Pb₃O₄）;白色颜料的显色成分为铅白（PbCO₃）和石灰石（CaCO₃）;粉色颜料的主要显色成分为铅丹和铅白的混合物;青色颜料为铜绿（Cu₂（OH）₂CO₃）和青石（Cu₃（OH）₂（CO₃）₂）混合物。     

The removal of Th,Cs and Sr ions from solution using granulated pumice stone

The removal of Sr, Cs, U and Th ions from aqueous solution by means of natural pumice stone was studied using energy dispersive X-ray fluorescence spectroscopy (EDXRF) as an analytical tool. The results indicate the usefulness of pumice powder and the removal efficiency was found to be in order of Th>Sr>Cs ions, which is altered by the pH of the solution.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

X-ray spectrometry using polycapillary X-ray optics and position sensitive detector

Polycapillary X-ray optics (capillary X-ray lens) are now popular in X-ray fluorescence (XRF) analysis. Such an X-ray lens can collect X-rays emitted from an X-ray source in a large solid angle and form a very intense X-ray microbeam which is very convenient for microbeam X-ray fluorescence (MXRF) analysis giving low minimum detection limits (MDLs) in energy dispersive X-ray fluorescence (EDXRF). A new method called position sensitive X-ray spectrometry (PSXS) which combines an X-ray lens used to form an intense XRF source and a position sensitive detector (PSD) used for wavelength dispersive spectrometry (WDS) measurement was developed recently in the X-ray Optics Laboratory of Institute of Low Energy Nuclear Physics (ILENP) at Beijing Normal University. Such a method can give high energy and spacial resolution and high detection efficiency simultaneously. A short view of development of both the EDXRF using a capillary X-ray lens and the new PSXS is given in this paper.     

Analysis of nuclear materials by energy dispersive X-ray fluorescence and spectral effects of alpha decay

Energy dispersive X-ray fluorescence (EDXRF) spectra collected from alpha emitters are complicated by artifacts inherent to the alpha decay process, particularly when using portable instruments. For example, ²³⁹Pu EDXRF spectra exhibit a prominent uranium L X-ray emission peak series due to sample alpha decay rather than source-induced X-ray fluorescence. A portable EDXRF instrument was used to collect qualitative spectra from plutonium and americium, and metal alloy identification was performed on a Pu-contaminated steel sample. Significant alpha decay-induced X-ray fluorescence peaks were observed in spectra obtained from the plutonium and americium samples due to the ²³⁵U and ²³⁷Np daughters, respectively. The plutonium sample was also analyzed by wavelength dispersive XRF (WDXRF) to demonstrate that alpha decay-induced X-ray emission has a negligible effect on WDXRF spectra.     

Energy Dispersive X-Ray Fluorescence Analysis and X-Ray Microanalysis of Medieval Silver Coins

 Austrian medieval silver/copper coins were investigated at their surfaces by energy dispersive X-ray fluorescence analysis (EDXRF) and at the cross-sections by X-ray microanalysis in the scanning electron microscope (SEM/EDX) in order to estimate the error occurring when corroded objects of art and archaeology are analyzed on the surface by non-destructive methods. Additionally, Ag/Cu-standards were treated in diluted sulphuric acid and the depletion of copper on the surface was measured by EDXRF. By calculating the ratio of the Ag-K/Ag-L intensity the process of blanching could be studied.     

A non-invasive XRF study supported by multivariate statistical analysis and reflectance FTIR to assess the composition of modern painting materials

The palette used in two paintings by Paul Cézanne, L'étang des soeurs dated c. 1875 and La route tournante, made in the last year of his life (1902), were analyzed using non-invasive spectroscopic methods. X-ray fluorescence combined with principal components analysis (PCA) and supported by reflectance near- and mid-FTIR was shown to be a powerful analytical tool to draw conclusions about the chemical identification of inorganic materials in paintings. Pigments and fillers such us Thénard's blue, Prussian blue, red ochre, kaolin, vermilion, lead white, zinc white and barium sulphate, were identified. Evidence for three different pigments, namely a copper arsenite pigment, chrome green (a mixture of chrome yellow and Prussian blue) and viridian has been obtained by the PCA analysis of elemental compositions of green hues.     

Analysis and Protection of One Thousand Hand Buddha in Dazu Stone Sculptures

The components of the rock, the pigments, the gold foils and the adhesive of One Thousand Hand Buddha in Dazu stone sculptures, Chongqing, China, have been analyzed by X-ray diffraction (XRD), X-ray fluorescence (XRF), infrared spectroscopy (IR), energy dispersive X-ray analysis (EDX) and fiber optics reflectance spectroscopy (FORS). Furthermore, the weathering and degeneration of One Thousand Hand Buddha have been discussed and the protective methods have been provided. In this work some useful information to study on conservation of stone relics is given.     

Towards the identification of plant and animal binders on Australian stone knives

There is limited information regarding the nature of plant and animal residues used as adhesives, fixatives and pigments found on Australian Aboriginal artefacts. This paper reports the use of FTIR in combination with the chemometric tools principal component analysis (PCA) and hierarchical clustering (HC) for the analysis and identification of Australian plant and animal fixatives on Australian stone artefacts. Ten different plant and animal residues were able to be discriminated from each other at a species level by combining FTIR spectroscopy with the chemometric data analysis methods, principal component analysis (PCA) and hierarchical clustering (HC). Application of this method to residues from three broken stone knives from the collections of the South Australian Museum indicated that two of the handles of knives were likely to have contained beeswax as the fixative whilst Spinifex resin was the probable binder on the third.     

Raman microscopy of Greek icons: identification of unusual pigments

Five Greek icons, made between the 15th and 18th centuries and now belonging to the Victoria and Albert Museum collections, were analysed by energy-dispersive X-ray fluorescence (EDXRF), optical microscopy and Raman microscopy in order to determine the stratigraphy of the artworks and the identity of the pigments used. Together with common pigments, such as red lake, vermilion, red lead, red iron oxide, orpiment, yellow ochre, lead white, chalk, gypsum, anhydrite, Prussian blue, indigo and a copper-containing green, a few unusual materials were identified, specifically pararealgar (a yellow arsenic sulphide, As4S4), its precursor the chi-phase, and lead tin yellow type II (PbSn(1-x)SixO3). Attention is drawn to the complementarity of the techniques used for the pigment identifications.     

Soil characterization by energy dispersive X-ray fluorescence: sampling strategy for in situ analysis.

This work describes a sampling strategy that will allow the use of portable EDXRF (energy dispersive X-ray fluorescence) instruments for "in situ" soil analysis. The methodology covers a general approach to planning field investigations for any type of environmental studies and it was applied for a soil characterization study in the zone of Campana, Argentina, by evaluating data coming from an EDXRF spectrometer with a radioisotope excitation source. Simulating non-treated sampled as "in situ" samples and a soil characterization for Campana area was intended. "In situ" EDXRF methodology is a powerful analytical modality with the advantage of providing data immediately, allowing a fast general screening of the soil composition.     

Non-invasive identification of chemical compounds by energy dispersive X-ray fluorescence spectrometry, combined with chemometric methods of data evaluation

Chemicals from customers' returns have to be analyzed before they can be reused as raw materials in production. A procedure for non-invasive qualitative analysis of compounds in a closed container based on energy dispersive X-ray fluorescence (EDXRF) spectrometry is described. EDXRF was chosen as method for noninvasive analysis of chemicals through PE bottle walls without opening the bottle. This analysis aims for a quick proof of correspondence between the declaration of a reagent on the label of the bottle and its content. This analytical result cannot be achieved by a mere evaluation of characteristic element lines in EDXRF-spectra in combination with the method of matrix correction or the method of mean atomic number. These methods take into account only a small part of the total information available in an X-ray spectrum. It is shown here that valuable additional information is extractable from the spectral ranges of the Compton-scattering and Rayleigh-scattering areas by the use of methods of multivariate data analysis, especially by principle component analysis (PCA). Regularized discriminant analysis (RDA) was employed to establish a classification scheme for unknown samples.     

Rapid identification of inorganic salts using energy dispersive X-ray fluorescence.

A simple method for the rapid identification of inorganic salts used as raw materials during food production has been established using energy dispersive X-ray fluorescence (EDXRF). Intensities of Na, Mg, P, S, Cl, K, Ca, Mn, Fe, Cu, Zn Kalpha peaks have been measured. The treatment and comparison of the respective intensities allowed a rapid identification of inorganic salts. Two different methods of data treatment have been tested: K nearest neighbours (KNN) and centroids. Using cross validation on a database containing 140 samples representing 31 classes, a total of 98% of samples were well identified.     

Non-invasive identification of chemical compounds by energy dispersive X-ray fluorescence spectrometry, combined with chemometric methods of data evaluation

Chemicals from customers’ returns have to be analyzed before they can be reused as raw materials in production. A procedure for non-invasive qualitative analysis of compounds in a closed container based on energy dispersive X-ray fluorescence (EDXRF) spectrometry is described. EDXRF was chosen as method for non-invasive analysis of chemicals through PE bottle walls without opening the bottle. This analysis aims for a quick proof of correspondence between the declaration of a reagent on the label of the bottle and its content. This analytical result cannot be achieved by a mere evaluation of characteristic element lines in EDXRF-spectra in combination with the method of matrix correction or the method of mean atomic number. These methods take into account only a small part of the total information available in an X-ray spectrum. It is shown here that valuable additional information is extractable from the spectral ranges of the Compton-scattering and Rayleigh-scattering areas by the use of methods of multivariate data analysis, especially by principle component analysis (PCA). Regularized discriminant analysis (RDA) was employed to establish a classification scheme for unknown samples.