X-ray fluorescent analysis on Indo-Pacific glass beads from Sungai Mas archaeological sites,Kedah, Malaysia

Sungai Mas was an ancient port-kingdom located on West Coast of Peninsula Malaysia in a district of Kota Kuala Muda, Kedah, Malaysia. The port-kingdom evolved as an entrepot since fifth century AD and continuously visited by international trader from India, China, Middle East and Europe until eighteenth century AD. Sungai Mas was also one of the Indo-Pacific beads making centers in Southeast Asia since sixth to thirteenth century AD and also produced pottery and brick. X-ray fluorescent analysis (XRF) on Sungai Mas Indo-Pacific beads is carried out to determine whether the glass beads originated from Arikamedu, India or locally made by community in Sungai Mas. Totally, twenty-two samples of beads and beads materials assayed by XRF were chosen. Contents of nine major elements and nine trace elements, which might be present of flux, stabilizer, colorants or opacifier were examined. The elements Si, Na, K, Ca, Fe, Al, Ti, Mn, Mg, Cu, Pb, Zr, Sr, Ba, La, U, Ni and Cr were detectable in all samples. The concentration of elements found are discussed in terms of flux, silica or lead base glass, color and/or opacity of the glass beads and glass samples. The result showed that Sungai Mas produced their own Indo-Pacific beads from sixth to thirteenth century AD.     

XAS study on copper red in ancient glass beads from Thailand

Glass has been used in ornaments and decorations in Thailand for thousands of years, being discovered in several archeological sites and preserved in museums throughout the country. To date only a few of them have been examined by conventional methods for their compositions and colorations. In this work we report for the first time an advanced structural analysis of Thai ancient glass beads using synchrotron X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray (EDX) spectrometry. Four samples of ancient glass beads were selected from four different archeological sites in three southern provinces (Ranong, Krabi and Pang-nga) of Thailand. Archaeological dating indicated that they were made more than 1,300 years ago. A historically known method for obtaining a red color is to add compounds containing transition elements such as gold, copper, and chromium. For our samples, EDX spectrometry data revealed existing fractions of iron, copper, zinc, and chromium in ascending order. Thus, copper was selectively studied by XAS as being potentially responsible for the red color in the glass beads. K-shell X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of copper were recorded in fluorescence mode using an advanced 13-element germanium detector. Comparisons with XANES spectra of reference compounds identified two major forms of copper, monovalent copper and a metallic cluster, dispersed in the glass matrix. The cluster dimension was approximated on the basis of structural modeling and a theoretical XANES calculation. As a complement, EXAFS spectra were analyzed to determine the first-shell coordination around copper. XAS was proven to be an outstanding, advanced technique that can be applied to study nondestructively archaeological objects to understand their characteristics and how they were produced in ancient times.     

XRF study of archaeological and metallurgical material from an ancient copper-smelting site near Ein-Yahav, Israel

A movable XRF instrument (a bench-top designed machine modified to work in the field for archaeological purposes) was used for analysis of artifacts and sediments during the field study (01–07 April 2003) of a small copper-smelting site in the Negev (about 30 km west of the Feinan complex of ancient copper mines and smelting sites in Jordan). The site consists of a relatively small hill with blackened slopes, covered mainly by crushed copper slag. The surface collection of datable objects (i.e. pottery shards and stone tools) indicated that the site had functioned at the end of the Early Bronze Age and during the Roman/Byzantine time.

The analysis of Cu concentration in the ash and in the ground as well as the analysis of ore and slag, were used as markers for the identification of the operation centers and for locating the remains of the smelting devices used at the end of the Early Bronze Age for smelting copper. The ore in use typically contained 35–45% Cu, up to 1% Mn and up to several percent Fe. The slag contained 13–20% Mn and 1–5% Cu and Fe. From these results we are able to estimate the Cu production scale during the first and most active period on this site, at the end of the Early Bronze Age.     

INAA,AAS, and lead isotope analysis of ancient lead anchors from the Black Sea

Lead stocks of wooden-lead anchors found along the Bulgarian Black Sea coast and typologically dated VI c. B.C.-III c. A. D. have been analyzed for chemical composition and lead isotope ratios by INAA, AAS and mass spectrometry. Using multivariate methods for analysis as well as simple bivariate plots the lead for production of the stocks was localized as originating from Laurion, Thassos, Troas, Chalkidike and the Rhodopes. In general, the chemical composition is not recommended to be used for provenance study of lead artefacts. Combining the results from this study with the existing typological classification certain conclusions about the production and distribution of lead anchors in the Aegean region are made.     

Determination of optimum conditions for INAA of archaeological clay figurines

In order to obtain sufficiently accurate results for the provenance characterization of ceramic objects, the error risks are studies at each step of the instrumental neutron activatin analysis. The homogeneity of clay figurines and the reproductibility of the analytical process are tested. For the sampling, a weight of 100 mg is enough to obtain significant results. The use of the K₀ Standardization Method and a well specified position during the radioactive measurements, improve the precision of the element determinations. The experimental conditions chosen are described and the accuracy of the method is tested on international standards.     

Combined elemental analysis of ancient glass beads by means of ion beam,portable XRF,and EPMA techniques

Ion beam analysis (IBA)- and X-ray fluorescence (XRF)-based techniques have been well adopted in cultural-heritage-related analytical studies covering a wide range of diagnostic role, i.e., from screening purposes up to full quantitative characterization. In this work, a systematic research was carried out towards the identification and evaluation of the advantages and the limitations of laboratory-based (IBA, electron probe microanalyzer) and portable (milli-XRF and micro-XRF) techniques. The study focused on the analysis of an Archaic glass bead collection recently excavated from the city of Thebes (mainland, Greece), in order to suggest an optimized and synergistic analytical methodology for similar studies and to assess the reliability of the quantification procedure of analyses conducted in particular by portable XRF spectrometers. All the employed analytical techniques and methodologies proved efficient to provide in a consistent way characterization of the glass bead composition, with analytical range and sensitivity depending on the particular technique. The obtained compositional data suggest a solid basis for the understanding of the main technological features related to the raw major and minor materials utilized for the manufacture of the Thebian ancient glass bead collection.     

INAA of Aegaean pumices for the classification of archaeological findings

Instrumental neutron activation analysis (INAA) was used to determine 29 elements in pumice from several volcanic sources (Milos, Nisyros, Yali, Kos and Thera) in the Aegean Sea, Greece, to establish a data basis for the identification of pumice and tephra layers found in archaeological context. The widespread products of the “Minoan Eruption” of the Thera volcano can now be distinguished clearly from all other sources and will be used to establish a datumline in the Eastern Mediterranean Region in the second millenium B.C. The elements Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Sm, Ta, Ti, Th, U, V, Yb and Zr were determined in 14 samples from Milos, 25 samples from Nisyros, 7 samples from Yali, 7 samples from Kos and 17 samples from Thera. Two cycles of irradiation and four measurement runs were applied. The results were compared and suitable groups, typical for each island, were classified. Due to insufficiently comparable data sets, the criteria for distinguishing the different sources have not been revealed by previous studies. This basic knowledge was used to relate pumice from excavations in Tell-el-Dab'a (Egypt) and Bronze Age Knossos to their specific volcanic origin.     

Application of INAA in analysis of Chinese ancient greenish white porcelain

This paper reports the applications of INAA in analysis of Chinese ancient porcelain fired from early Northern Song dynasty (AD 1004–1127) to Late Yuan dynasty (AD 1320–1368) in Hutian Kiln. Minor and trace elements of 168 pieces of ancient porcelain bodies were determined by INAA. The results of factor analysis and some archaeological questions are also discussed in this paper.     

A standardless approach of INAA for grouping study of ancient potteries

The k ₀ based internal monostandard neutron activation analysis was used to analyze 41 ancient pottery samples from three major locations of Andhra Pradesh state, India, belonging to two different age groups namely Megalithic and Buddhist periods. Samples were irradiated with neutron flux obtained from CIRUS reactor and radioactive assay was carried out using a 40% relative efficiency HPGe detector coupled to 8?k MCA. Concentration ratios of 21 elements were calculated with respect to internal monostandard Sc. Absolute concentrations for six (three each from both Megalithic and Buddhist periods) representative samples along with a modern pottery were obtained for comparison. Elemental concentration ratios with respect to Sc were used for grouping of these archaeological samples. Preliminary grouping of these artifacts was done using La/Ce values, and the grouping was confirmed by statistical cluster analysis using eleven selected trace elements. The IAEA RM SL-3 sample was analysed for validation of the method, where in both concentration ratios and absolute concentrations were calculated.     

Magnetic and chemical characterization of black pottery from Hanseong Baekje archaeological site,South Korea

Journal of Radioanalytical and Nuclear Chemistry - The black pottery unearthed from the Hanseong Baekje archaeological site in Seoul, South Korea was characterized by type using different...     

INAA of Minoan ceramics from Kommos,Crete

A recent study concerning the deviation of the E^–(1+) epithermal neutron flux distribution from the E^–1 law, developed by F. DE CORTE et al. is applied to -determination in different channels of the CRN reactor (Strasbourg). It is found that the coefficient is positive inside the reactor core and negative outside. The accuracy of the neutron activation analysis using the corrected resonance integral I() is tested.     

On the microporous structure of glass beads

Summary Glass beads of controlled porosity are interesting packings for chromatography. They are used as molecular sieves and they can constitute the starting point for the production of packings with a chemically bonded phase. From the practical point of view it would be desirable to known the methods for obtaining porous glass beads of strictly defined structure. In this communication attention will be drawn to the occurrence of microporous structure in glass beads, which is an unfavourable phenomenon from the standpoint of chromatography. Moreover, a method allowing us to remove the microporosity will also be discussed.     

Major and trace element characterization of prehistoric ceramic from Rezende archaeological site

Forty one ceramic fragment samples from Rezende archaeological site, Centralina city, Minas Gerais State, Brazil, were analyzed using INAA to determine the concentration of 24 chemical elements: As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn. Three multivariate statistical methods, cluster, discriminant and principal components analysis were performed on the data set. The results showed that the large majority of the samples (94%) can be considered to be manufactured using the same source of raw material.     

The use of INAA technique in provenance studies of ancient pottery from the Greater Accra region of Ghana

The field of Archaeological in Ghana has been in existence for a very long time, gaining respect in some areas in the West African sub-region. The history of some early societies in Ghana with relation to pottery making and its uses still has a lot to be discovered. Provenance or source analyses are vital in exchange studies by finding the sources of artifacts. Through characterization studies, archaeological materials can be shown to have originated from particular areas enabling archaeologists to demonstrate human interaction. The Ga (Ayawaso) and the Dangme-Shai had cultural contacts and trade with neighboring towns and with the various European factors that traded in the coasts of Accra. The archaeological material remains recovered from these communities (Ayawaso, Wullf and Shai) during excavation were investigated using Scientific Nuclear Analytical technique. In all, the concentrations of 15 trace elements (i.e. Ce, Co, Cr, Eu, Fe, Hf, La, Lu, Mn, Rb, Sc, Ta, Tb, V, Yb) were determined in 40 pottery samples and clay samples from Afuamang (Ayawaso) and Doryumu (Shai) using instrumental neutron activation analysis (INAA). Raw clay samples from Doryumu and Afuamang normalized perfectly with pottery samples from the Shai and Ayawaso Township, respectively. Pottery samples from Wullf also normalized well with clay from Afuamang than it did with those from Doryumu. This is construed that the Wullf community did not produced their own pots but traded more with the potters from Ayawaso which was the closest potting town.     

A multi-analytical approach for the characterization of powders from the Pompeii archaeological site

Nine black powders found in Pompeii houses in three different types of bronze vessels (cylindrical theca atramentaria, unguentaries, and aryballoi) were characterized in order to assess a correspondence between the composition and the type of vessel and, possibly, to verify if these powders were inks or not. For the compositional characterization, a multi-analytical approach was adopted, which involved the use of scanning electron microscopy-energy dispersive X-ray, Fourier-transformed infrared spectroscopy, Raman, X-ray diffraction, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, gas chromatography coupled with mass spectrometry (GC/MS), and pyrolysis GC/MS. Powders contained in cylindrical theca atramentaria form a homogeneous group, and their organic and inorganic compositions suggest that they were writing inks, while powders contained in unguentaries and aryballoi could have had several different uses, including writing inks and cosmetics. Furthermore, the composition profile of the powders found in cylindrical cases shows that, at 79?AD: , in Pompeii, carbon-based inks were still used for writing, and iron gall inks had not been introduced yet.     

Complex conductivity of water-saturated packs of glass beads

The low-frequency conductivity response of water-saturated packs of glass beads reflects a combination of two processes. One process corresponds to the polarization of the mineral/water interface coating the surface of the grains. The other process corresponds to the Maxwell-Wagner polarization associated with accumulation of the electrical charges in the pore space of the composite medium. A model of low-frequency conductivity dispersion is proposed. This model is connected to a triple-layer model of electrochemical processes occurring at the surface of silica. This model accounts for the partition of the counterions between the Stern and the diffuse layers. The polarization of the mineral/water interface is modeled by the electrochemical polarization model of Schurr for a spherical grain. We take into account also the DC surface conductivity contribution of protons of the sorbed water and the contribution of the diffuse layer. At the scale of a macroscopic representative elementary volume of the porous material, the electrochemical polarization of a single grain is convoluted with the grain size distribution of the porous material. Finally, the Maxwell-Wagner polarization is modeled using the complex conductivity of a granular porous medium obtained from the differential effective medium theory. The predictions of this model agree well with experimental data of spectral induced polarization. Two peaks are observed at low frequencies in the spectrum of the phase. The first peak corresponds to the distribution of the size of the beads and the second peak is due to the roughness of the grains.     

Characterization of the chemical composition of archaeological glass finds from South-Eastern Bulgaria using PIXE, PIGE and ICP-AES

Using PIXE (proton induced X-ray emission), PIGE (proton induced gamma emission) and ICP-AES (inductively coupled plasma-atomic emission spectroscopy) the concentrations of the 24 elements Al, As, Ba, Br, Ca, Cl, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Pb, Rb, S, Sb, Si, Sn, Sr, Ti, Zn and Zr in 53 archaeological glass samples from South-Eastern Bulgaria, were determined. The glasses are dated from the 1st to 6th century AD. The analytical data showed the samples to be typical soda-lime-silica glass, with natron as flux. A rather broad range of aluminium, titanium and iron impurities was found, with a tendency for more impure glass in the later periods. The decolouring agents were antimony and manganese oxides, with Sb prevailing in earlier, and Mn in later glass.     

Radioisotope x-ray fluorescence analysis of ancient pottery from Tel Kouzama site in Damascus, Syria

The radioisotope X-ray fluorescence method has been utilized in the analysis of thirty nine archaeological pottery fragment samples from Tel Kouzama site, Damascus city, Syria. The samples were irradiated by a 109Cd radioisotope source (-9 10(8) Bq) for 1000 s. 17 chemical elements were determined. These elemental concentrations have been processed using two multivariate statistical methods, cluster and factor analysis in order to determine similarities and correlation between the various samples. Factor analysis confirms that samples were correctly classified by cluster analysis. These two methods suggest that samples can be considered to be manufactured using four different sources of raw material.     

Immobilization of several multienzyme systems on porous glass beads

Equimolar concentrations of malate dehydrogenase (EC 1.1.1.37) and fumarase (EC 4.2.1.2) and equimolar concentrations of malate dehydrogenase and citrate synthase (EC 4.1.3.7) were simultaneously immobilized to alkylamine porous silica beads with gluteraldehyde. The activity of each enzyme in the two-enzyme immobilized systems was determined and exact concentrations of the free nonimmobilized enzymes were prepared. The activities of the coupled free and coupled immobilized systems were measured, and it was observed that there was a 10-fold enhancement in the catalysis of the immobilized enzymes.     

Correlations between chemical composition and provenance of Justino site ceramics by INAA

Instrumental neutron activation analysis (INAA), have been used for the definition of compositional groups of potteries from Justino site, Brazil, according to the chemical similarities of ceramic paste. The outliers were identified by means of robust Mahalanobis distance. The temper effect in the ceramic paste was studied by means of modified Mahalanobis filter. The results were interpreted by means of cluster, principal components, and discriminant analyses. This work provides contributions for the reconstruction of the prehistory of baixo São Francisco region, and for the reconstitution of the Brazilian Northeast ceramist population of general frame.