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 on ancient Chinese imitated GE ware by INAA and WDXRF

Imitated GE ware was one of the most famous products of Jingdezhen porcelain field in Ming dynasty (AD 1368-1644). The exterior features of its body and glaze are very marvelous. Black foot, purple mouth and crazing glaze are the main features of imitated GE ware. Until now, the key conditions of resulting these features are not clearly identified. In order to find the critical elements for firing these features, instrumental neutron activation analysis (INAA) and wavelength-dispersive X-ray fluorescence (WDXRF) were used to determine the element abundance patterns of imitated GE ware body and glaze. The experimental data was compared with that of imitated Longquan celadon and of Longquan celadon. The analytical results indicated that Fe, Ti and Na were the critical elements. The body of imitated GE ware which contains high Fe and Ti are the basic conditions of firing its black body, black foot and purple mouth. The glaze of imitated GE ware which contains high Na is the main condition of producing its crazing glaze. Na is the critical element which enlarges the difference in expansion coefficients between the glaze and body of imitated GE ware. Furthermore, Zijin soil was added into kaolin to make the body rich in Fe and Ti. And something which was rich in Na was used to produce crazing glaze in the manufacturing process of imitated GE ware.     

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.     

Chemical shift measurements of chlorine K X-ray spectra using a high-resolution PIXE system

A high-efficiency high-resolution wavelength-dispersive spectrograph with a von-Hamos configuration was developed for chemical state identification of elements in environmental samples using PIXE analysis. To evaluate the performance of this system, chlorine K X-ray spectra for NaCl, NH₄Cl and polyvinylchloride (PVC) targets were measured and compared. Also, to study the applicability to environmental mixed samples, mixtures of NaCl and NH₄Cl with different mixing ratios were measured. Through observation of Cl Kα₁ X-ray from NaCl, the energy resolution of the system was determined to be 1.1 eV. For the NaCl sample, a Kβ_x line was observed at an energy, which is higher than that of the Kβ main peak by 2 eV, whereas no Kβ_x emission was observed for the NH₄Cl sample. The chemical shift of the Kβ main peak for PVC relative to that for NaCl was about 1.2 eV. For NaCl-NH₄Cl mixture targets, the relative intensity of Kβ_x satellite to the Kβ main line provided an indication of mixing ratio. Energies and relative intensity of Cl Kβ X-ray satellites for NaCl and NH₄Cl samples calculated by a simple molecular-orbital method agreed only qualitatively with the experimental results.     

Towards more precise Be and Cl data from measurements at the 10 level: Influence of sample preparation

The spreading application of accelerator mass spectrometry (AMS) to the geosciences will require measurement of increasing numbers of samples with low ¹⁰Be/⁹Be and ³⁶Cl/Cl isotopic ratios. To distinguish radionuclide concentrations in samples from corresponding processing blanks, samples must be prepared using stable isotope carriers with low intrinsic radionuclide concentrations. Measurements at different AMS facilities have shown that commercially available ⁹Be carriers rarely meet these requirements and use of ⁹Be carriers prepared from Be-containing minerals such as Be₂SiO₄ is advisable. For precise determinations at the low 10⁻¹⁴ level, samples need to produce the highest ⁹Be currents possible. Measurements performed at the two AMS facilities in France show that mixing BeO with Nb powder generally yields higher ⁹Be currents than mixing with Ag powder. Contamination of BeO by other elements such as Ti or Al will reduce the current by a simple dilution effect, thus limiting the statistical precision with which ¹⁰Be can be determined. In the case of ³⁶Cl analyses, repeated water-leaching of calcite samples sufficiently removes all atmospheric ³⁶Cl contamination, allowing determination of terrestrial cosmogenic in situ produced ³⁶Cl concentrations for surface exposure dating.     

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.     

PIXE analysis of obsidian tools from radiocarbon dated archaeological contexts

Obsidian tools from archaeological sites in Turkey and Southern Italy, ¹⁴C-AMS dated to the Neolithic were submitted to IBA analyses at CEDAD, University of Salento, Italy. PIXE and PIGE quantitative analysis of major and trace elements allowed the separation of the samples in different compositional groups corresponding to different sources of obsidian, identified on the basis of published data.     

Chemical characterization of ancient pottery from the greater Accra region of Ghana using neutron activation analysis

Archaeology in Ghana has a long and respectable tradition. Despite this encouraging situation, significant gaps still exist in our understanding of the history of some early societies in Ghana. Accumulated evidence revealed that the Ga (Ayawaso), Dangme-Shai and the Wullf had trade and other cultural contacts with their Akan and Guan neighbours as well as the various European factors that traded and established footholds in the Accra coast. In an attempt to reconstruct the early history of the Ga, Dangme-Shai and Wullf, the archaeological material remains recovered from these communities during excavation have been studied. In all, 15 trace elements were determined in 40 pottery shards using instrumental neutron activation analysis. The elemental concentrations were processed using multivariate statistical methods, such as cluster, factor and discriminant analyses. The results revealed patterns of trade between these communities and also classified the 40 samples into two major groups based on variations in elemental compositions. The groupings suggested a clear separation between the shards from Shai and Ayawaso. The shards from Wullf scattered amongst the two groups, consistent with the archaeological findings that the Wullf community never produced their own pots.     

Analysis of activation products generated from photoneutron capture reactions inside a linear accelerator used in a cargo inspection facility

Activation products are generated from photoneutron capture reactions inside a linear accelerator (LINAC) used in a high energy X-ray cargo inspection facility. The activation products are estimated using MCNPX, Monte Carlo simulation code, in order to evaluate radiological safety in the facility. The result shows that the maximum radiation dose rate from the saturated activity in LINAC room is about 2.18E−06 Sv/h and 74-W-187 is the most significant radionuclide generated. It is, therefore, recommended that a proper measure to reduce the radionuclide is considered to protect occupational workers against the decay radiations.     

IBA analyses and lead concentration measurements of AMS-C dated bones from two medieval sites in Italy

AMS (accelerator mass spectrometry) radiocarbon dated human bone samples recovered in the deserted medieval village of Quattro Macine, Lecce, in Southern Italy, were analyzed by PIXE (particle induced X-ray emission) and PIGE (particle induced gamma ray emission). The optimization of the PIXE-PIGE experimental set-up in term of beam energy and detection geometry resulted in the possibility to obtain information about major, minor and trace elements of the samples. Unexpectedly, all the analyzed samples showed a Pb concentration higher than 50 ppm. Two possible explanations of the measured high Pb concentration are discussed in the paper: the pre-mortem intake associated with the use of Pb-rich glazed pottery and the post-mortem intake from soil as the result of diagenetic processes.     

PIXE characterization of Lebanese excavated amphorae from Jiyeh archeological site

Archaeological excavations were undertaken in the Jiyeh archeological site which is located north of Sidon, identified as the Greco-Roman Porphyreon. The first investigations raised suggest a probable pottery production centre. About 40 sherds were analyzed by Proton Induce X-ray Emission technique PIXE in order to identify and characterize the elemental composition of four types of amphorae, using the 1.7 MV tandem accelerator in Beirut. The analysis protocol provided almost 24 elements in one spectrum, including majors, minors and traces. The elemental composition provided by PIXE and based on 12 most abundant elements, ranging from Mg to Zr, was used in a multivariate statistical program and consequently the studied objects were classify into well defined groups.     

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.     

External micro-PIXE analysis of fluid inclusions: Test of the LABEC facility on samples of quartz veins from Apuan Alps (Italy)

Fluid inclusions are small portions, usually smaller than 100 μm, of fluid trapped within minerals during or after growth. Their characteristics provide therefore fundamental information on nature and evolution of fluids present in the past in different geological environments. At the LABEC laboratory in Firenze, high-salinity fluid inclusions in quartz crystals, coming from the Apuan Alps metamorphic complex, were analysed at the external scanning microbeam. Results, although still preliminary, have already provided us with hints on fluid-rock interaction processes during the metamorphism of the Apuan Alps.     

AMS radiocarbon dating of medieval textile relics: The frocks and the pillow of St. Francis of Assisi

Since natural textiles usually originate from short-lived organisms, they can represent a useful material to date samples from historical periods with a good accuracy.In this work, we present a set of radiocarbon measurements on medieval textile relics: two woollen habits and a pillow traditionally associated with St. Francis of Assisi, the saint patron of Italy. The strategy in choosing samples for radiocarbon dating is first discussed and the procedures for measurements - performed at the 3 MV Tandetron accelerator of Laboratorio di Tecniche Nucleari per i Beni Culturali (LABEC), Florence - are described; AMS results for the two frocks showed that only one of them, presently kept in the church of St. Francis in Cortona, is compatible with the Saint’s period of life, as is the pillow also kept in Cortona. Another frock attributed to St. Francis appears to date from at least 80 years after his death. However, the goal of these measurements was not a bare authentication/disconfirmation of the relics; they just represent an example of how scientific analysis can integrate with humanistic studies. Indeed, AMS results, combined with a thorough analysis of the textiles typologies, confirmed the historical hypotheses based on documentary studies and on tradition. The overall conclusions contributed to the decisions taken for conservation, and have as a whole enhanced the religious importance of the relics.     

Studies of effect of deposition parameters on the ZnO films prepared by PLD

Thin films of zinc oxide (ZnO), having different thicknesses were prepared by pulsed laser deposition (PLD) technique onto silicon Si(1 1 1) and quartz (SiO₂) substrates at different partial pressures of oxygen. Rutherford back scattering (RBS) analysis was carried out in order to investigate effect of deposition parameters on thickness of films. Quality of the films was investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM) analyses. The thickness of the film was found to increase with oxygen partial pressure for both Si and SiO₂ substrates.     

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.     

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.     

Micro-PIXE-RBS methods highlighting the influence of phosphorus on the in vitro bioactivity of sol-gel derived glass particles in the SiO2-CaO-P2O5 system

Ion beam analysis methods were used to characterize the interface of bioactive glasses with surrounding biological fluids. Glass particles in the SiO₂-CaO and SiO₂-CaO-P₂O₅ compositions were made by sol-gel processing and soaked in biological fluids for periods up to 4 days. The surface changes were characterized using PIXE-RBS, which are efficient methods for multielemental analysis and accurate trace elements quantification. Elemental maps of major and trace elements were obtained at a micrometer scale and revealed the bone bonding ability of the materials. Glass particles are quickly coated with a thin calcium phosphate-rich layer containing traces of magnesium. After a few days, SiO₂-CaO-P₂O₅ glass particles are entirely changed into calcium phosphates, whereas SiO₂-CaO particles exhibit a different behavior: the previously Ca-P enriched periphery has been dissolved and glass particles consist of a silicate network. Calculation of the Ca-P atomic ratios at the glass/biological fluids interface provides us with an explanation for this: an enduring apatitic phase seems to be formed at the periphery of SiO₂-CaO-P₂O₅ glass particles. Presence of phosphorus in the glass matrix thus has an influence on the amplitude and the kinetics of reaction of the bioactivity process. It might result in an improved chemical bond with living tissues.     

Proton beam writing and electroplating for the fabrication of high aspect ratio Au microstructures

We present an approach to fabricate tall high aspect ratio Au microstructures by means of proton beam direct writing. Combining proton beam direct writing and electroplating, we successfully produced gold structures with sub-micrometer lateral dimensions, structure heights in excess of 11 μm, and aspect ratios over 28. Sidewall quality of the Au structures was improved by lowering the process temperature to 20 °C when developing PMMA patterns with GG developer. The application of such structures as X-ray masks for deep X-ray lithography with synchrotron radiation was demonstrated.     

MeV-ion beam analysis of the interface between filtered cathodic arc-deposited a-carbon and single crystalline silicon

Amorphous carbon (a-C) films were deposited on Si(1 0 0) wafers by a filtered cathodic vacuum arc (FCVA) plasma source. A negative electrical bias was applied to the silicon substrate in order to control the incident energy of carbon ions. Effects of the electrical bias on the a-C/Si interface characteristics were investigated by using standard Rutherford backscattering spectrometry (RBS) in the channeling mode with 2.1-MeV He²⁺ ions. The shape of the Si surface peaks of the RBS/channeling spectra reflects the degree of interface disorder due to atomic displacement from the bulk position of the Si crystal. Details of the analysis method developed are described. It was found that the width of the a-C/Si interface increases linearly with the substrate bias voltage but not the thickness of the a-C film.