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A contribution to the discussion about Vila Nova de São Pedro (VNSP) as a production centre of symbolic lithic artefacts, the origin of raw materials, as well the comparison with similar artefacts from other Chalcolithic sites are the major goals. For the first time, non-destructive analytical methods were employed to obtain a detailed chemical characterization of these remarkable artefacts. The results point to its production mainly with local raw material. This work enhances the understanding of the trade routes of raw materials and objects from the “production centre” of VNSP during the Chalcolithic.

Portuguese museums and private collectors gather a variety of Italian glazed terracotta sculptures attributed to the della Robbia workshop, particularly active between the 15th and 16th centuries. Compositional studies of the paste using INAA, PGAA and XRD and enamel using PIXE, and luminescence protocols, were used as a tool to ascertain the attribution of the sculptures to della Robbia workshop. Geochemical and mineralogical patterns were defined enabling to express the production recipe. The luminescence ages were found to be between 1380 and 1640 in some cases with high uncertainties. The compositions of the blue glazes were proved to be similar to other measured on della Robbia sculptures from French and Italian collections based on cobalt pigments. Arsenic behaviour, which is associated to cobalt in most cobalt-minerals, is rather peculiar, as it was already found in other della Robbia sculptures enabling a chronological framework, pointing to a production after 1520. Based on the results, most of the analysed sculptures implies a della Robbia production, and only a few point to a composition and chronology not related with that workshop. Fundação para a Ciência e a Tecnologia support through the UID/Multi/04349/2013 and PTDC/HIS/HEC/116742/2010 projects; H2020 CHARISMA funded (Grant Agreement no. 228330) project at Budapest Neutron Center; FB, MNAA, MNAz, FCG, MJ for sampling and field measurements. info:eu-repo/semantics/publishedVersion

External milli-beam particle induced X-ray emission spectroscopy (PIXE) has been used as non-destructive technique to investigate ancient linen fabrics from pre-dynastic and Ptolemaic ages belonging to the archaeological collections of the Egyptian Museum of Turin and to the Civic Archaeological Museum of Bologna, Italy. 9 linen fabric samples dated from Old Kingdom to Ptolemaic ages (2200-300 B.C.) were investigated, as well as 5 modern linen fabric samples, added for comparison. The primary goal of this work has been to advance the correct material description of the fabrics providing scientific data for further and more comprehensive comparative analyses. PIXE has provided quantitative analyses for the major (Si, Cl, K, Ca and Fe) and minor or trace elements as P, Ti and Mn, supplying information on the near-surface elemental composition. The achieved results contribute to comprehend the structural basis for the chemical properties of the considered materials, as well as to set up a classification according to the chemical composition, allowing in general a better understanding of the studied linen cloths.

Non-destructive prompt gamma activation analysis (PGAA), neutron radiography (NR) and high resolution time-of-flight neutron diffraction (TOF-ND) have been applied to investigate metal archaeological artefacts belonging to the Academia Georgica Treiensis (AGT) collection. 8 archaeological items have been analysed, by using the facilities of the Budapest Neutron Centre (BNC). Some of these objects mostly dating back probably to the VI-IV century B.C. and presumed to be discovered in the Marche Region, Italy. The primary goal of the analyses was to advance the correct technological and material description of the objects, providing scientific data for further and more comprehensive comparative analyses also covering the find material from the close archaeological sites. The neutron investigations allowed determining the bulk composition, also providing either a qualitative and quantitative assessment of the phase composition and the structural properties of the constituents, or radiographic images, which would finally help to identify possible manufacturing techniques. Additional examinations, carried out by external milli-beam particle induced X-ray emission spectroscopy (PIXE), provided quantitative analyses of major and trace elements (e.g., Fe, Pb and As) in order to recognize the constitutive alloys and to supply information on the near-surface elemental composition, complementary to the data characteristic for the bulk. The obtained results, thought to be useful to set up a classification according to the chemical composition, and this way allow achieving important information related to the possible provenance of the objects.

The objective of this study is to find out, to what extent the geochemical characteristics of lapis lazuli can be utilized in respect to its provenance. A wide range of variables is taken into consideration depending on the quantity of samples analysed from a specific geological region and the methods applied. In order to provide evidence, a multi-technique analytical approach using µXRF, ESEM, PGAA and PIXE is applied to samples from the most famous deposits of lapis lazuli. Special elements determined as fingerprints are compared in relation to the forming conditions obvious in textural features. The results and statistical output allow a differentiation that enables an optimized local classification of the blue stone. An absolute requirement for all geo-tracing performed on blue colored cultural objects of unknown provenance is awareness of the limits of analysis. The possible sources of lapis lazuli are tested by analysing the blue pigment used as paint on murals and ink on manuscripts from the Silk Road.

Les recherches sur le patrimoine culturel utilisant les méthodes neutroniques et à faisceaux d’ions au centre de neutrons de Budapest présentées ici mettent l’accent sur les applications fructueuses réalisées dans la cadre du programme européen CHARISMA. Cultural Heritage experiments in synergy with neutron-based and ion beam techniques at the Budapest Neutron Centre are presented, with special emphasis to successful applications within the CHARISMA project

Combined external milli-beam Particle Induced X-ray Emission (PIXE) and Prompt Gamma Activation Analysis (PGAA) analysis was applied to characterize the composition of paste and colorants from some fragments of Byzantine bracelets (10th–12th Centuries AD), late medieval (17th–18th Centuries AD) and modern Murano glass pieces. As fluxes, PGAA revealed the samples are soda-lime glass, except four samples - two medieval vessel white shards and two dark Byzantine fragments of bracelets – which have potash flux. Aluminium was detected in various proportions in all samples indicating different sources for the added sand. The presence of Magnesium is relevant only in one bracelet fragment suggesting the use of plant (wood?) ash and confirming that the Byzantine bracelet is manufactured from the mixture of both types of glass (natron and plant ash based). PGAA also indicated the presence of low quantities of Cadmium, high level of Arsenic and Lead (possibly lead arsenate) in one medieval sample and of ZnO in Murano glass, and of CoO traces (maximum 0.1%) in all blue-colored Byzantine, late medieval to modern Murano glass artefacts. PIXE confirmed the use of small quantities of CoO for blue color, indicated Manganese combined with Iron for dark glass, Copper for green, Lead, Tin and an Arsenic compound (orpiment?) for yellow and in the case of modern Murano glass Selenium and Cadmium to obtain a reddish color. Despite PIXE – PIGE combination is probably the best one for glass analysis, our external milli-PIXE – PGAA methods proved to be adequate complementary tools to determine many chemical elements from glass composition – Si, Na, K, Ca, Al, Mg, various metallic oxides.

A set of beads was studied to investigate their nature. They come from a funerary feature used for the secondary deposition of cremated remains of more than a hundred individuals. The pit is located in the centre of Perdigoes (Evora, Portugal) ditched enclosures (Valera et al., 2014a) and is dated from the third quarter of the 3rd millennium BC. The beads were also burned and were part of the funerary votive assemblages, also composed by arrowheads ivory figurines, marble idols and pots, phalanx idols, copper awls, Pecten shells and pottery sherds. These beads have a diameter between 5 and 10.5 mm, with a central perforation up to 5 mm and maximum thickness of 3 mm, they are dark grey or black and were of unknown nature. This study shows that these beads were made from shells and submitted to heating processes. The study demonstrates the ability of neutron and X-ray methods to determine the nature of the material even being very calcium rich. Chemical results show that they have high contents of calcium, and that the surface is more contaminated with soil particles due to high Si, Fe and K contents, and phosphorous was found in higher proportion, certainly originated from the bones. FTIR patterns show that the major part of the beads is calcium carbonate crystallized in calcite form, contaminated with silicates and calcium phosphate, pointing to shells as raw materials. The ToF-ND results also indicate the crystal lattice structure of calcite, and aragonite, a polymorph formed in the biomineralisation process of shells, was not detected, indicating a total phase transformation to calcite probably due to heating processes during funerary practices. The SEM-EDS results confirm the shell nature of beads. The results were of wider significance for the archaeological discussion, especially deciphering the nature of the beads, contributing to the debate of interaction in the Chalcolithic of Southern Iberia.

Non-invasive, archaeometric analyses on selected Hungarian Bronze Age defensive armour is presented here: three greaves, three helmets two shields as well as one vessel fragment were analysed with PIXE, PGAA and TOF-ND. The detected alloy elemental and phase composition as well as its intergranular or spatial concentration distribution reveals important insights into the alloys used and the manufacturing techniques applied c. 1200–950 BC, and allows to reconstruct the production techniques used during the Late Bronze Age.

External beam milli-PIXE technique was used for the determination of the elemental concentration ratios in some Prehistoric obsidian tools found in Transylvania, in the Iron Gates region near Danube, as well as on a few relevant geological obsidian samples from Slovak Tokaj Mountains, Lipari, Armenia. As provenance “fingerprints” the Ti to Mn and Rb to Zr ratios were used. The results confirm that the Transylvanian Neolithic samples have a Slovak Tokaj Mountains provenance. For Iron Gates samples, there are at least two different geological sources: for Late Neolithic tools, the origin is also the Slovak Tokaj Mountains but for Late Mesolithic–Early Neolithic samples, the sources are clearly different, possibly of the Hungarian Tokaj Mountains or the Balkan–Aegean origin.

Metal content of metalloproteins can be detected and even quantified by the PIXE–PAGE method. In this technique the proteins are separated by thin layer electrophoresis (by polyacrylamide gel electrophoresis (PAGE) in most cases) and the properly dried gel sections are analyzed by PIXE using “band-shaped” proton milli-beam. This PIXE–PAGE method was adapted for our scanning proton microprobe. The microPIXE–PAGE version provides two-dimensional elemental mapping of the protein bands. In addition, the fast continuous scanning reduces the risk of the thermal deterioration of the sample and the X-ray contribution from dust-impurities can be filtered out in the data evaluation process.

A new scanning proton microprobe has been installed at the 5 MV Van de Graaff accelerator of the KFKI Research Institute for Particle and Nuclear Physics. It is the energy-upgraded version of the Hamburg proton microprobe dismantled in 2001. The probe forming system includes a pair of focusing quadrupoles and an additional quadrupole pair in front of it, which is applied to increase the proton beam divergence. The average probe size at 2.5 MeV proton energy is 2.2 μm × 1.1 μm. The test results on stability and the preliminary experiments on cement corrosion and fish otoliths are also presented.

Six rather different bronze archaeological artefacts discovered over time in the Tifernum Mataurense area (S. Angelo in Vado, Marche Region, Italy) did not fit by visual inspection to the findings collected in nearby archaeological sites and they differ from each other, too. The primary goal of this work was to obtain data from the elemental composition of using a fast non-destructive quantitative analytical method. To do that the external milli-beam particle induced X-ray emission spectroscopy (external milli-beam PIXE) was chosen. Taking into account that not any invasive actions as burnishing, scratching or chemical treatment were allowed and the surface of the objects was rather corroded or patinated, the results obtained can be considered to be rather informative, only. Even these informative results, however, are useful to set up a classification of the objects according to the chemical composition and provide complementary near-surface composition information to the bulk data expected from cold neutron PGAA analyses to be performed.

The permissible level of the Pb content in wine varies in the range of 200–300 μg/l in different countries. These values are below the detection limit for standard PIXE spectrometry. Initiated by an intercomparison action of The International Measurement Evaluation Programme (IMEP, Geel, Belgium), an attempt was made to lower the detection limit of PIXE without introducing any additional chemical steps. Wine samples of 5 ml were gradually condensed below an infrared lamp and 8 μl aliquots were taken from time to time and pipetted onto filter paper. The samples were analysed by standard PIXE technique, with the analyte addition method used for calibration. A detection limit of about 50 ppb was finally achieved. Comparing this value to the permissible levels, this simple and fast technique can be used for screening purposes. As an application, the lead content of three Hungarian market wines was also measured.

The earliest known iron artefacts are nine small beads securely dated to circa 3200 BC, from two burials in Gerzeh, northern Egypt. We show that these beads were made from meteoritic iron, and shaped by careful hammering the metal into thin sheets before rolling them into tubes. The study demonstrates the ability of neutron and X-ray methods to determine the nature of the material even after complete corrosion of the iron metal. The iron beads were strung into a necklace together with other exotic minerals such as lapis lazuli, gold and carnelian, revealing the status of meteoritic iron as a special material on a par with precious metal and gem stones. The results confirm that already in the fourth millennium BC metalworkers had mastered the smithing of meteoritic iron, an iron–nickel alloy much harder and more brittle than the more commonly worked copper. This is of wider significance as it demonstrates that metalworkers had already nearly two millennia of experience to hot-work meteoritic iron when iron smelting was introduced. This knowledge was essential for the development of iron smelting, which produced metal in a solid state process and hence depended on this ability in order to replace copper and bronze as the main utilitarian metals.

An interesting and unique glass drinking cup can be found in the Medieval Archaeological Collection of the Istvan Dobo Castle Museum in Eger, originating from Karoly Kozak's (OMF – National Inspectorate of Historic Monuments1) excavations at Eger Castle, from a site located to the south of the Romanesque Cathedral. The find came to light on October 14, 1977.