Pre-Columbian alloys from the royal tombs of Sipán and from the Museum of Sicán. Non-destructive XRF analysis with a portable equipment (original) (raw)
X-Ray Spectrometry
Energy dispersive X-ray fluorescence (EDXRF) is widely used in the study of archeological metal artifacts, heritage and art history, where the fragile nature of the objects requires the use of noninvasive techniques such as the EDXRF, which in addition, is fast and very affordable.An EDXRF analysis of copper-based artifacts from Late Bronze Age metal hoards from Central Portugal is presented.The EDXRF measurements were carried out by using an X-ray tube with a Mo anode and a commercial Si-PIN detector. The data acquisition was performed by keeping small distances between the X-ray window, the sample and the detector. Both patinated and polished areas were analyzed: the relative composition of the artifacts was inferred from the fluorescence spectra obtained. Copyright © 2012 John Wiley & Sons, Ltd.
X‐Ray …, 2009
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 nondestructive 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.
ICOM-CC 17th Triennial Conference Preprints, Melbourne, 15–19 September 2014, 2014
Falling costs, smaller sizes and increasingly user friendly interfaces have led to the wide use of handheld portable x-ray fluorescence instruments (HHpXRF) in the analyses of cultural heritage objects. Methodological considerations on the validity of results derived from HHpXRF have led to debates in conservation and archaeological literature. Relatively little attention has been paid to the applicability of HHpXRF to the characterisation of archaeological copper alloys. This paper evaluates the use of Bruker AXS Tracer III-SD on a range of certified copper alloys which were selected based on their occurrence in antiquity. Alloys were then electrochemically corroded and analysed to examine the impact of corrosion layers on HHpXRF data. Qualitative and quantitative data processing methods are compared and the impact of source to-sample distance on the HHpXRF results is examined. The implications and relevance of data accuracy are discussed with regard to archaeological interpretation and uses in conservation. The tables from this paper can be downloaded as spreadsheets from: https://www.researchgate.net/publication/266564964\_Testing\_the\_applicability\_of\_handheld\_portable\_XRF\_to\_the\_characterisation\_of\_archaeological\_copper\_alloys
X-ray analysis of objects of art and archaeology
Journal of Radioanalytical and Nuclear …, 2001
Some theoretical aspects and limitations of XRF are discussed, including information depths in layered materials, characterization of inhomogeneous specimens, light element analysis, and radiation damage. Worked examples of applications of XRF and XRD are pigment analysis in delicate Chinese Paper, corrosion of glass, and leaching effects in soil-buried medieval coins.
On the north coast of present-day Peru, between the Andes and the Pacific Ocean, prospered approximately between 1000 BC and 1375 AD, several relevant cultures: Chavín (1000-200 BC), Vicús and Frías (200 BC -300 AD), Moche (400 BC-700 AD), Sicán (700-1375 AD). These cultures are interconnected and characterized by a high metallurgical ability, demonstrated by the presence of beautiful artifacts on gold, silver and copper alloys. More than hundred metal artefacts from these cultures were analyzed with a portable equipment which uses the non-destructive and non-invasive technique of energy-dispersive X-ray fluorescence (EDXRF). Following objects were analyzed: (1) gold, silver and copper objects from the Chavín culture (Museo Municipal of Piura and and Museo Enrico Poli in Lima); (2) gold and silver objects from the Vicús and Frías cultures (Museo Municipal of Piura); (3) gold, silver and copper objects from the Moche culture ("Museo Tumbas Reales de Sipán", "Museo de Sitio de Huaca Rajada" in Lambayeque and Museo Enrico Poli in Lima); (4) gold, silver and copper objects from the Sicán culture (Museum of Sicán, Ferrañafe). Portable equipments were employed, mainly composed of a small size X-ray tube and a thermoelectrically cooled, small size, Si-PIN or Si-drift X-ray detectors. The main characteristics of the EDXRF-technique is of being non destructive and multi-elemental. Standard samples of gold and silver alloys were employed for calibration and quantitative analysis. The aims of this campaign of analysis were:
Archaeologia Baltica, 2023
This article discusses the results of a large-scale analysis of five cultural heritage alloy reference materials (CHARM) and their shavings using handheld (pXRF) and stationary energy dispersive (ED-XRF) spectrometers. The primary objective of these studies was to assess the capability of the pXRF and ED-XRF spectrometers as a non-invasive surface-measuring technique used for the analysis of the reference materials and the reliability of the data obtained. The second objective was to evaluate the capability of the pXRF and ED-XRF spectrometers used for the analysis of shavings of the same five reference materials and to assess the data obtained. These objectives required finding the best fitting analytical tools for the comparison, and the assessment of the reliability of the data, and, very importantly, finding reliable models for data analysis and results validity verification. Based on the analysis carried out on the cultural heritage alloy reference materials, it can be concluded that the results of XRF spectrometry obtained from both spectrometers are reliable and can be compared to each other by making reference to four basic conditions: that the provided analysis should be based on certified reference materials of known elemental composition; that analysis be performed according to appropriate measuring methodology (research protocol); that analysing tools (predictive analytics) be clearly defined; and, finally, that testing be done on archaeological artefacts. The reliability and inter-correlation of the results obtained were assessed to determine the possibility of successfully applying XRF spectrometry in the investigation of archaeological artefacts produced from copper alloys.
Pre-Columbian alloys from the royal tombs of Sipán and from the Museum of Sicán
ArchéoSciences, 2009
Revue d'archéométrie 33 | 2009 Authentication and analysis of goldwork Pre-Columbian alloys from the royal tombs of Sipán and from the Museum of Sicán Non-destructive XRF analysis with a portable equipment Alliages précolombiens des tombes royales de Sipán et du musée de Sicán : analyse non-destructive avec un système FX portable
Portable energy-dispersive X-ray fluorescence equipment for the analysis of cultural heritage
Pramana, 2011
A portable EDXRF equipment was used to perform a qualitative and a quantitative in situ analysis of in natura water. Using this equipment 10 mL of water was directly analyzed. Detection limits, in mg L-1, for Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Hg and Pb were 12.5, 7.5, 4.9, 2.7, 2.8, 2.1, 1.6, 1.9, 3.4, 3.7, respectively, with deviation around 10%. In real samples, Fe, Zn and Pb were identifi ed. Given the obtained results, the analytical system performance appeared to be promising Key words: portable XRF; water; in natura; metal.
NON-DESTRUCTIVE ANALYSIS OF ANCIENT METAL ALLOYS BY IN SITU EDXRF TRANSPORTABLE EQUIPMENT
The availability of transportable equipment for in situ non-destructive analysis of works of art is considered to be very important. In situ non-destructive study is typically diagnostic, therefore requiring only qualitative or semiquantitative results. In the case of alloys, quantitative results can also be obtained. In Energy Dispersive X-Ray Fluorescence (EDXRF) analysis, portable instruments can now be assembled. For instance, miniaturised X-ray tubes with air cooling and high resolution semicon ductor detectors thermoelectrically cooled are now available, allowing the construction of completely transportable apparatus for EDXRF analysis. In this work, aspects regarding methodology of analysis and discussion of the precision obtainable in analysis of ancient metals are presented.
Analysis of Sagunto Ibero-Roman votive bronze statuettes by portable X-ray fluorescence
Radiation Physics and Chemistry, 2019
The main objective of this work was the study of chemical composition of an important collection of Ibero-Roman votive bronze statuettes exposed in the Archaeological Museum of Sagunto (Spain). Precision and accuracy of the measurements were obtained developing a proper analytical method, also avoiding any possible damage to the studied objects using a portable energy dispersive X-ray fluorescence system. Principal Components Analysis (PCA) to discriminate between groups based on ratios Fe/Cu, Pb/Cu, Sn/Cu, Ag/Cu, Ni/Cu and Impurities/Cu were employed to observe differences between the used smelting, manufacturing processes and raw materials. The characterisation of bronze statuettes cross-referenced with archaeological data, gave important suggestions to clarify issues regarding manufacturing processes, quality and chronologies of the studied objects.
Archaeometry, 2001
The use of a new analytical technique for the elemental characterization of artefacts is described. The new equipment is capable of X-ray¯uorescence analysis in conventional mode as well as for elemental scanning of small objects, fragments or microsamples. The Omicron, manufactured by Kevex Instruments Inc., is equipped with a microfocused X-ray tube, which can be collimated to a 50 mm beam and used to scan objects over a maximum range of 2562 56 pixels. False-colour elemental distribution maps allow the user to image small features, differently pigmented areas, or whole objects in the machine completely non-destructively. Analyses can be carried out in air, under helium or in vacuum. Two examples of the application of the new technique are described: ®rst, to the surface decoration on a Greek Attic white ground lekythos; and, second, to the pigments used on a small painting, à Pittura', on copper by the Dutch artist, Frans van Mieris (1635±81) in the collections of the J. Paul Getty Museum.
Combined non-destructive XRF and SR-XAS study of archaeological artefacts
Analytical and Bioanalytical Chemistry, 2011
We report on a non-destructive study of Sicilian ceramic fragments of cultural heritage interest, classified as "proto-majolica" pottery and dating back to the twelfth to thirteen centuries AD. The analytical approach used is based on the employment of two totally non-invasive spectroscopic techniques: X-ray fluorescence (XRF), using a portable energy-dispersive XRF analyser, and X-ray absorption spectroscopy, using synchrotron radiation as a probe (SR-XAS). XRF measurements allowed us to collect elemental and spatially resolved information on major and minor constituents of the decorated coating of archaeological pottery fragments, so providing preliminary results on the main components characterizing the surface. In particular, we assigned to Fe and Mn the role of key elements of the colouring agent. With the aim of obtaining more detailed information, we performed SR-XAS measurements at the Fe and Mn K-edges at the Italian BM08 beamline at the European Synchrotron Radiation Facility (Grenoble, France). The experimental data were analysed by applying principal component analysis and least-squares fitting to the near-edge part of the spectra (X-ray absorption near-edge structure) to determine the samples' speciation. From the overall results, umber, a class of brownish pigments characterized by a mixture of hydrated iron and manganese oxides, has been ascribed as a pigmenting agent.
Characterization of Castellani nineteenth-century gold jewellery by in situ micro-XRF spectroscopy
Scientific Reports, 2022
The material characterization of nineteenth-century artifacts is of great interest, due both to the breakthrough technological advances and to the unprecedented spread of forgeries of antiquities which took place in that period. However, this type of artifacts has been largely overlooked in the past. In this paper we present the compositional analysis of gold jewels by the Castellani, one of the most important families of goldsmiths in nineteenth-century Europe. The use of a portable micro-XRF spectrometer, specifically developed for jewellery analysis at the Centro Nacional de Aceleradores (Seville), allowed us to analyse, in a completely non-invasive way, the alloys, joining techniques and surface treatments of the jewels of the Castellani collection at the National Etruscan Museum of Villa Giulia in Rome. The addition to the spectrometer of a second X-rays detector with a zinc filter allowed us to check the possible presence of low amounts of cadmium, a metal added to gold soldering only from the nineteenth century and often used in authenticity studies. Moreover, the relative intensities of the Au X-ray lines were studied in order to check non-invasively the presence of surface enrichments in gold.
X-ray tomography and spectroscopy applications for revealing ancient metalworking techniques
Elsevier, 2025
This study investigates two pieces of ancient jewellery excavated from the Nerkin Naver Burial Mound and the Teishebaini Necropolis in Armenia. These sites are associated with the Middle Bronze Age and the Urartian Kingdom, respectively. XRF and X-ray μCT analyses were used to study the excavated artefacts. The application of these techniques revealed specific characteristics of the material composition and provided a deeper understanding of the metalworking methods used in the fabrication of these artefacts. This article is part of a special issue entitled: Channeling 2024 published in Nuclear Inst. and Methods in Physics Research, A.
Archaeometry, 1996
Celtic glasses of different colors, opaque or transparent, in the form of beautiful ornaments were characterized according to elemental composition by energy-dispersive x-ray fluorescence analysis. This analytical technique is nearly non-destructive and was the method of choice for this project. The Celtic glasses were loaned for the time of analysis by museums and private collections under the guarantee that no harm would be done to the objects. The main goal was to establish a reliable analytical method to achieve qualitative and quantitative results within acceptable errors. The historical and physical background is given and describes the motivation for this task. Preliminary tests carried out before the series measurements started are described and show that within a certain error range good results can be expected from samples of different shapes, with uneven or rough surfaces. Experimental conditions for the determination of light elements and subsequent extension to medium-and high-Z elements are described. The results from the test studies and for selected samples with various colors and shapes are presented.
X-rays in art and archaeology: An overview
Powder Diffraction, 2004
An overview of the techniques used in art and archaeology is presented and the applicability of X-ray radiography, X-ray fluorescence (XRF), and X-ray diffraction analysis (XRD) as a tool for nondestructive investigations of objects of art and archaeology is discussed. X-ray radiography, for example, is a standard technique widely used and accepted by art historians, archaeologists, curators, and conservators as this method enables information about the manufacturing process and the condition of an object without “touching” the artifact. XRF and XRD enable a nondestructive determination of the material composition of artifacts and the determination of the crystalline structure of the components too. Air path systems and instruments with the micro-beam of X-ray and synchrotron radiation were applied for the analysis of easel paintings, pigments in paint layers, glass artifacts, and coins.