Plating of archaeological metallic objects - studies by differential PIXE

The differential PIXE method using an external proton beam up to 3 MeV energy was applied to examine plated layers of tin, silver and gold on bronze, brass, iron and silver objects from Roman and Early Medieval period. The concentration profiles were deduced from the measurements by the method of virtual slicing the target into layers, and minimizing the differences between the measured and calculated X-ray yields. The tinned layers were usually thin (about 1 μm), but the thickness of silver and gold layers was in several cases thicker and exceeded the proton range. The plating techniques were identified as application of the molten metal for tinning, and as fire gilding for the gilded objects.     

Effects of the behaviour of the proton-induced isotopes production on the analysis of ancient alloys

The present work concerns non-destructive ion beam analysis carried out by means of proton-beam-induced nuclear reactions in the 10-30 MeV energy range. We focused our attention on the yield distribution of the isotopes produced in the internal region of a metal alloy. This distribution, which defines the analytical region, displays, at incident energy of about 20 MeV in a bronze based alloy, a bell-shaped curve centred at about 600 μm with an average width of about 400 μm. By changing the incident proton energy it is possible to displace the above region in the interior of the metal body. It should be pointed out that if we neglect to take into account the correct behaviour of the isotope yield distribution in samples with surface inhomogeneities we can obtain erroneous analytical results. We describe some experiments based on proton activation analysis (PAA) carried out at the INFN-Laboratori Nazionali del Sud (LNS) in Catania where we verified the bell-shape of the radioactive isotope distribution. The resulting formulas are given for quantitative analysis.It is straightforward that, by choosing the appropriate incident proton energy, it is possible to confine the whole analytical region to the interior of the body, thus eliminating any influence of surface effects. We have called this particular approach deep proton activation analysis (DPAA). Examples of its use on archaeological artefacts are given.     

Use of silicon drift detectors for the detection of medium-light elements in PIXE

In order to fully exploit in PIXE the superior performance of silicon drift detectors especially for the detection of low- and medium-energy X-rays, avoiding in particular the negative effects of backscattered particles, we developed a custom spectrometer based on a 10 mm² chip with a thermoelectric Peltier cooler and home-designed front-end electronics, coupled to a weakly focusing polycapillary lens.This paper briefly describes the detector + lens assembly and reports the results of first tests carried out at an external beam line of the LABEC laboratory in Florence. Excellent energy resolution is achieved under real operating conditions in a PIXE run (measured FWHM at 1 keV is 81 eV with a count-rate of 480 cps) and also the lineshapes are very good (FW1/10M over FWHM ratio is 2.1). As a whole, our preliminary tests gave encouraging results and also helped to point out some aspects which it is worthwhile to investigate further (e.g. how X-ray peak intensity ratios may be affected by inaccurate lens alignment), in order to profit fully from such a good performance of the spectrometer.     

The new Cyclone 18/9 beam transport line at the CNA (Sevilla) for high energy PIXE applications

The Cyclone 18/9 cyclotron system at the Centro Nacional de Aceleradores (Sevilla, Spain) is commonly used to create short life radioisotopes for PET applications. Besides, an external beam transport line has been recently installed in one of the target ports with two major purposes: to study the effects of 18 MeV protons irradiation on the behaviour of electronic devices for space applications and to complement the analysis of materials using our 3 MV tandem accelerator with the PIXE measurements at high energy.In this work, the main elements of our beamline will be briefly described and the first PIXE application will be presented. The usual PIXE, in the analysis of archaeological metallic objects, using around 3 MeV protons requires having a shiny area. Our purpose is to obtain a deeper determination of the bulk composition bombarding with 18 MeV protons through the corroded samples surfaces, without polishing the ancient object. To check this methodology high energy PIXE has been performed on two fibulae of the Later Bronze Age and First Iron Age, coming from the area around Sevilla.     

The micro-imaging station of the TopoTomo beamline at the ANKA synchrotron light source

The TopoTomo bending magnet beamline at the ANKA synchrotron facility in Karlsruhe (Germany) operates in the hard X-ray regime (above 6 keV). Recently, an X-ray micro-imaging station has been installed at TopoTomo. For typical imaging applications, a filtered white beam or from 2009 on a double-multilayer monochromator is used. In order to optimize the field of view and the resolution of the available indirect pixel detectors, different optical systems have been installed, adapted, respectively, to a large field of view (macroscope) and to high spatial resolution (microscope). They can be combined with different camera systems, ranging from 14-bit dynamic range CCDs to fast CMOS cameras. The spatial resolution can be brought substantially beyond the micrometer limit by using a Bragg magnifier. Due to the moderate flux of the beamline compared to insertion-device beamlines on third generation light sources, special emphasis has been put on the efficiency of the detectors via a dedicated scintillator concept. The layout of the beamline optics makes optimal use of the coherence properties. Thus, absorption contrast, phase-contrast and analyzer-based imaging can be applied. Additionally, white beam synchrotron topography is performed, using digital indirect X-ray pixel detectors as well as X-ray film.     

IBA characterisation of glasses from the archaeological site of “La Alcazaba”, Almería (Spain)

“La Alcazaba de Almería” is one of the most impressive mediaeval remains in Al-Andalus. It was the sea port of the Córdoba Caliphate and, afterwards, the capital of a “Taifa” kingdom. In the course of recent excavations in this monumental area, several glass remains were found in the access to its palace and were dated back to the XIII-XV centuries, during the so-called “Nazarí” period.We have made PIGE and PIXE analysis of different fragments of these glasses in order to identify their composition versus the different colours and shapes. These analyses have been complemented with other techniques, like SEM in order to learn about the corrosion process suffered by these glasses during their long burial period. Also a comparison with ICP-OES has been made to check the validity of the IBA results in this case where we are dealing with corroded samples.     

Study of the provenance of Belgian Merovingian garnets by PIXE at IPNAS cyclotron

Recent archaeological excavation in Belgium reveals one of the biggest Merovingian necropolis ever found in this country. This necropolis contains 436 tombs with a period of occupation of almost two centuries. Some of these tombs were very rich, especially two of them, and delivered an important funerary furniture. About 60 jewels inlaid with red garnets have been found, most of them of “cloisonné” style (namely about 450 garnets). The new extracted beam set-up of the IPNAS cyclotron (University of Liège, Belgium) has been improved in order to analyse by PIXE these garnets and try to determine their provenance. These analyses reveal that the garnets found in the necropolis of Grez-Doiceau are very homogeneous in composition (almandine garnets) and are coming almost from a unique source.These results have been compared to previous studies led in France during these past five years. This permits to identify the source of almandine garnet situated in India and to highlight differences in garnet supply between France and Belgium in Merovingian times.     

Micro-SR-XRF and micro-PIXE studies for archaeological gold identification - The case of Carpathian (Transylvanian) gold and of Dacian bracelets

Trace-elements are more significant for provenancing archaeological metallic artifacts than the main components. For gold, the most promising elements are platinum group elements (PGE), Sn, Te, Sb, Hg and Pb. Several small fragments of natural Transylvanian gold - placer and primary - were studied by using micro-PIXE technique at the Legnaro National Laboratory AN2000 microbeam facility, Italy and at the AGLAE accelerator, C2RMF, Paris, France and by using micro synchrotron radiation X-ray fluorescence (micro-SR-XRF) at BESSY synchrotron, Berlin, Germany. The goal of the study was to identify the trace-elements, especially Sn, Sb and Te. A spectacular application to five Dacian gold bracelets authentication is presented (Sn and Sb traces).     

In situ ERDA measurements of hydrogen isotope concentrations in palladium at atmospheric pressure

In situ elastic recoil detection analysis (ERDA) measurements in gases at atmospheric pressure have been carried out using 15 MeV ⁴He ion beams. The beams are extracted through a molybdenum foil having a thickness of 5 μm. The maximum depth of analysis is about 4 μm for the palladium hydride and palladium deuteride (PdH_x and PdD_x, x = 0.7-0.8) samples. The temperature of the samples rises stepwise from room temperature to 180 °C. ERDA spectra are obtained every 2 min. Hydrogen and deuterium in the samples are discharged in the temperature range of 120-140 °C in a vacuum. Decrease in the hydrogen concentration in the PdH_x sample heated in a vacuum follows a first order in the value of x and an apparent activation energy of discharge of hydrogen is 1.05 eV. On the other hand, the hydrogen and deuterium concentrations decrease at about 80 °C in air. No isotope effects are observed in both a vacuum and air. The temperature at which the hydrogen concentration decreases in helium gas is almost the same as that in a vacuum. It indicates that hydrogen and deuterium atoms are discharged by chemical reactions with air and that there are no effects of cooling of the thermocouple by convection of air.     

Study on the elemental features of ancient Chinese white porcelain at Jingdezhen by INAA

Shards of ancient Chinese white porcelain, which were excavated at Maojiawan in the city of Beijing, were analyzed by instrumental neutron activation analysis (INAA). These shards were fired in the period between the Yuan (AD 1271-1368) and Ming (AD 1368-1644) dynasties at Jingdezhen in southern China. According to the analytical results, different raw materials were used for making porcelain body in this period. Fe and Na are the characteristic elements which can be used for identifying the specific date of these porcelains. Furthermore, shards of Hongwu era (AD 1368-1398), Yongle-Xuande era (AD 1403-1435) and Chenghua-Zhengde era (AD 1465-1561) of the Ming dynasty can be clearly distinguished by their elemental body composition. The temporal chemical variation in the porcelain body of these eras is observed. The elemental body composition of Zhengde-Tianshun era (AD 1436-1464) is mainly similar to that of the Hongwu and Yongle-Xuande eras. The temporal chemical feature of Zhengtong-Tianshun era was not found.     

Study of new sheep bone and Zn/Ca ratio around TiAlV screw: PIXE-RBS analysis

This study reports on in vivo particle induced X-ray emission (PIXE) measurements combined with Rutherford backscattering spectroscopy (RBS) analyses of new remodeled sheep bone formed around TiAlV screws. The implants (screws) were anodized by a modified TiMax™ process. The interface between the implant and the bone was carefully investigated. [Zn]/[Ca] in-depth composition profiles as well as Ca, Fe elemental maps were recorded. The thickness of new bone formed around the screw reached 300-400 μm. Osteon and Osteoid phases were identified in the new bone. A higher [Zn]/[Ca] ratio was observed in the new bone as compared to the mature bone. Blood vessels were observed in the bone in close contact with the screw.This study shows the potential of ion beam analysis for biological and biomedical characterization.     

Compositional studies on Transylvanian gold nuggets: Advantages and limitations of PIXE-PIGE analysis

Minute fragments from nine gold nuggets from Transylvania - two belonging to placer deposits and seven to primary deposits - were analyzed by PIXE and PIGE at the AGLAE tandem accelerator of the Centre de Recherche et de Restauration des Musées de France (C2RMF) with a 3 MeV proton beam extracted into air. This study was triggered by some archaeological provenance issues for which the elemental characterization of the Transylvanian gold source, exploited from the Antiquity, was required. All analyzed Transylvanian gold nuggets are characterized by a consistently high amount of Ag (18% on average). Au and Ag add up to roughly 99%, the other elements - Cu, Fe, Te, Pb - being detected only at a trace level. The obtained results are in good agreement with the previous analyses of Transylvanian gold.     

PIXE and XRF analysis of particulate matter samples: an inter-laboratory comparison

PIXE and XRF are very effective techniques in atmospheric aerosol investigation, therefore they are extensively used by the authors. In this work an inter-laboratory comparison of the results obtained analysing several samples (collected on different substrata) with both techniques is presented: the samples were analysed by PIXE (in Florence, at the 3 MV Tandetron accelerator of LABEC laboratory) and by XRF (in Genoa and Milan, where two Oxford XRF instruments are operational). The results of the three sets of measurements are in good agreement for all the analysed samples.The aim of this work was also to compare PIXE and XRF performance in atmospheric aerosol analysis with the routine set-up currently in use at the three laboratories, to determine the best technique to be applied depending on the substratum used for aerosol sampling and the main elements of interest for each specific research project. Results of the comparison between the minimum detection limits of both techniques will be shown for all the measured elements, for different substrata (Teflon, polycarbonate and cellulose mixed esters).     

Biomonitoring study of seasonal anthropogenic influence at the Itamambuca beach (SP, Brazil)

The present work is focused on the study of a seasonal anthropogenic influence on the beach of Itamambuca (Ubatuba, SP, Brazil) carried out using Atherinella brasiliensis as biomonitor. In total 84 fish were caught between July 2004 and February 2005 in different locations at the beach and inside the Itamambuca river. The fish were pooled according to catch and their musculature was analyzed by Particle-Induced X-ray Emission (PIXE) and Rutherford Backscattering (RBS) techniques. While the concentration of light (matrix) elements like C and O were obtained using the RBS technique, major (Na, Mg, P, S, Cl, K and Ca) and trace (Si, Al, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br and Sr) elements were measured by PIXE. The results show that differences were observed for several elemental concentrations of fish tissue between high season (spring-summer) and low season (winter-fall), indicating that increased human activity in the beach during high season may have some impact on the beach ecosystem. The role of the water salinity in the results is also discussed.     

PIXE and PIGE techniques for the analysis of Antarctic ice dust and continental sediments

An analytical procedure has been implemented in this work for an accurate geochemical characterization and quantitative analysis of the fine dust (particles diameter < 5 μm) trapped in Antarctic ice cores and the fine fraction of potential source areas (PSA) sediments by size selection, filtering and PIXE-PIGE combined measurements. The underestimation of concentrations of the lighter elements, like Na, Mg, Al and Si, due to X-ray self-absorption inside each individual aerosol particle, was also evaluated and the analytical overall accuracy tested by means of measurements performed on size selected certified mineral standards.     

Cell irradiation setup and dosimetry for radiobiological studies at ELBE

The radiation source ELBE delivers different types of secondary radiation, which is used for cell irradiation studies in radiobiological research. Thereby an important issue is the determination of the biological effectiveness of photon radiation as a function of photon energy by using low-energetic, monochromatic channeling radiation (10-100 keV) and high-energetic bremsstrahlung (up to 40 MV). Radiobiological studies at the research facility ELBE demand special technical and dosimetric prerequisites. Therefore, a cell irradiation system (CIS) has been designed, constructed and installed at the beam line. The CIS allows automatic irradiation of a larger cell sample number and the compensation of spatial inhomogeneity of the dose distribution within the beam spot. The recently introduced GafChromic^® EBT radiochromic film model has been used to verify the cell irradiation dose deposition achieving a dose uncertainty of <5%. Both, the installed cell irradiation system and the developed dosimetric procedure based on the use of the EBT film have been experimentally tested at ELBE. The biological effectiveness of 34 MV bremsstrahlung with respect to 200 kV X-rays from a conventional X-ray tube has been determined. An RBE value of 0.75 has been measured in good agreement with literature.     

A Time of Flight-Energy spectrometer for stopping power measurements in Heavy Ion-ERD analysis at iThemba LABS

The quantitative analysis of thin layers using Heavy Ion-Elastic Recoil Detection (HI-ERD) can be reliably performed if the stopping powers of the probing ions and recoils in a given target matrix are known accurately. Unfortunately for many projectile/target combinations experimental data is limited and where available, deviations of up to 50% between experiment and theory have been reported. This presentation describes the assembly of a Time of Flight-Energy (ToF-E) detector system developed for HI-ERD analysis and adapted for stopping power measurements at iThemba LABS. First results from energy loss measurements of 0.1-0.5 MeV/nucleon ²⁸Si and ⁸⁴Kr ions in ZrO₂ are presented and compared with predictions of the widely used SRIM2003 (Stopping Range of Ions in Matter).     

Differential and scanning-mode external PIXE for the analysis of the painting “Ritratto Trivulzio” by Antonello da Messina

Extensive PIXE investigations have been performed at the LABEC accelerator laboratory in Florence on the painting “Ritratto Trivulzio” by Antonello da Messina, one of the great Italian masters of XV Century and a pioneer in modern oil painting.It is well known that a complete and unambiguous characterisation of materials in paintings is often difficult, owing to their complex structure. For the “Ritratto Trivulzio”, the combination of advanced variants of PIXE, such as differential and scanning-mode analysis, provided a relevant contribution to the characterisation of paint layers, in terms of composition and structure, in a totally non-invasive and non-destructive way.Single-spot mode PIXE with external proton beams of about half millimetre diameter was first used for a general characterisation of different areas of the painting. Differential PIXE performed in many spots led to reconstruct the sequence of paints employed by the artist and to estimate in some cases the local paint layer thickness.A second run carried out with the external scanning microbeam facility, using a 3 MeV proton beam of about 80 μm size, was then crucial to clarify some issues raised by the first analysis. In particular, elemental maps from selected areas helped to understand the way some colour shades had been obtained on the red mantle of the portrayed gentleman, using different pigments irregularly distributed on the surface.     

A 3D-RBS study of irradiation-induced deformation and masking properties of ordered colloidal nanoparticulate masks

The 500 keV Xe²⁺ irradiation-induced anisotropic deformation of ordered colloidal silica nanoparticulate masks is followed using 2 MeV ⁴He⁺ Rutherford Backscattering Spectrometry (RBS) with different measurement geometries and the improved data analysis capabilities of the RBS-MAST spectrum simulation code. The three-dimensional (3D) geometrical transformation from spherical to oblate ellipsoidal and polygonal shape and the decrease of the mask’s hole size is described. The masking properties of the silica monolayer and the depth distribution of Xe in the underlying Si substrate vs. the irradiated Xe²⁺ fluence are discussed. Field Emission Scanning Electron Microscopy (FESEM) is applied as complementary characterization tool. Our results give contribution to clarify the impact of ion-nanoparticle interactions on the potentials and limits of nanosphere lithography. We also show the capability of the conventional RBS technique to characterize laterally ordered submicron-sized three-dimensional structures.     

A DSP-based multichannel analyzer for simultaneous acquisition of coincidence and anticoincidence spectra

A digital signal processor (DSP) based multichannel analyzer (MCA) has been developed for simultaneous acquisition of coincidence and anticoincidence γ-ray spectra. The shaped pulse from the spectroscopy amplifier is digitized by a flash analog-to-digital converter and then processed by a DSP. The coincidence mode operation is implemented by an external gate signal from a coincidence module. Fundamental performance was tested using NaI(Tl) detectors and compared with that of a standard NIM module. The new MCA is currently used for in vivo neutron activation analysis. Further development is in preparation toward full digital processing, which is free from the remaining analog component, that is the spectroscopy amplifier.