THE TRADING OF ANCIENT GLASS BEADS: NEW ANALYTICAL DATA FROM SOUTH ASIAN AND EAST AFRICAN SODA–ALUMINA GLASS BEADS*

The occurrence of similar glass beads at archaeological sites in Africa and Asia bears witness to the trade relationship between the two continents. This paper reports elemental analysis results from a recent in‐depth laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS) study of a group of archaeological glass beads with a specific alumina‐rich composition from East Africa, India and Sri Lanka. Based on the concentrations of the trace elements, two different subgroups were identified. One subgroup occurs at early periods (fourth century bce to fifth century ace ) in South India and Sri Lanka. The second subgroup appears at later dates in Africa and was identified at different Kenyan sites dated from the ninth to the 19th century ace , and at the contemporaneous site of Chaul in western India.     

A STUDY OF GLASS BEADS FROM THE HALLSTATT C–D FROM SOUTHWESTERN POLAND: IMPLICATIONS FOR GLASS TECHNOLOGY AND PROVENANCE*

Eighty‐one samples taken from 68 glass beads found in southwestern Poland on sites of the Lusatian culture from the Hallstatt C and Hallstatt D subphases were analysed by EPMA. A subsample of 18 of these were additionally subjected to analysis by means of LA–ICP–MS in order to validate the results obtained by EPMA. Some glass was made using mineral soda and some using plant ash rich in sodium. Both high‐magnesium soda–lime glass (HMG) and low‐magnesium soda–lime glass (LMG) were identified. A large number of samples are characterized by low MgO content and medium K₂O content (LMMK glass), combined with low concentrations of CaO and high Fe₂O₃ and Al₂O₃. All the LMMK glass contains numerous silica crystals and inclusions composed of a number of elements (most frequently Cu, Co, Sb, As, Ag, Ni and Fe). The LMMK glass was presumably made in Europe during the Hallstatt C.     

WASTE GLASS,VESSELS AND WINDOW‐PANES FROM THAMUSIDA (MOROCCO): GROUPING NATRON‐BASED BLUE–GREEN AND COLOURLESS ROMAN GLASSES

A collection of window‐panes, vessels and alleged waste from Thamusida has been investigated by OM, SEM–EDS, ICP–MS, ICP–OES and XAS at the Fe–K and Mn–K edges. Glass samples have been characterized as natron‐based soda–lime–silica glasses, with low magnesium and low potassium. The results have been compared with 43 reference groups available for ‘naturally coloured’ and colourless glasses of both Roman and later ages. Two main types were distinguished: RBGY 1 (R oman B lue–G reen and Y ellow 1) and RBGY 2 (R oman B lue–G reen and Y ellow 2). Given their compositional similarity to the Levantine I or, to a lesser extent, HIMT glasses, the Syrian–Palestinian coast for RBGY 2 and Egypt for the RBGY 1 have been suggested for their provenance. Most Thamusida samples have been assigned to the RBGY 2 type. A small group of Thamusida colourless vessels was included into the RC (R oman‐C olourless) compositional field; the latter still being defined. The alleged waste pieces may define a local production that should have been of secondary type. The investigations performed on local raw materials seem to discount the possibility of a primary glass‐making site. XAS measurements determined that Fe²⁺ contents ranging between 30 and 52% are able to assure an aqua blue colour; below 30%, the glasses turn light green or light yellow.     

MEDIEVAL LEAD GLASS IN CENTRAL EUROPE

In Trommsdorfstraße, Erfurt, a glass‐processing workshop has been excavated, which produced lead glass rings and beads in the 13th century. This workshop produced two different lead glasses. The first, a high‐lead glass, could be found throughout Europe, from England to Russia. However, another newly defined type of glass could be identified (Central European lead–ash glass). This can be demonstrated by analysing the literature, and it has been found in eastern Germany, Poland, Slovakia and the Czech Republic. A Slavic lead–ash glass with the same ash content as the Central European lead–ash glass but lower amounts of lead was produced in Eastern Europe. In western Germany, another type of ash (beech ash) was used to produce a wood‐ash lead glass. Lead‐isotope analysis proved that the same source of lead was used for the wood‐ash lead glass and the high‐lead glass in western Germany and the two types of glass from Erfurt.     

IDENTIFICATION OF POST‐DEPOSITIONAL CHEMICAL ALTERATION OF CERAMICS FROM THE NORTH COAST OF PAPUA NEW GUINEA (SANDUAN PROVINCE) BY TIME‐OF‐FLIGHT–LASER ABLATION–INDUCTIVELY COUPLED PLASMA–MASS SPECTROMETRY (TOF–LA–ICP–MS)*

The measured chemical composition of archaeological ceramics can result from a variety of geological, cultural and taphonomic factors. In the present study, we evaluate the likelihood that elevated barium concentrations in ceramics from the archaeological site of Wom/Aiser, located on the northern coast of Papua New Guinea, result from post‐depositional enrichment. Using time‐of‐flight–laser ablation–inductively coupled plasma–mass spectrometry, we mapped chemical compositional profiles across cut sections of ceramic sherds from four archaeological sites, all previously chemically characterized. We identify the formation of pronounced concentration gradients in samples from Wom/Aiser relative to sherds with low barium concentrations, consistent with post‐burial uptake.     

AN ARCHAEOMETRIC STUDY OF MEDIEVAL GLASS FROM THE FIRST BULGARIAN CAPITAL,PLISKA (NINTH TO TENTH CENTURY AD)

Glass finds from the first Bulgarian capital, Pliska, have been analysed by instrumental neutron activation analysis. The analytical data, together with previous results from analysis of glass samples from the second Bulgarian capital, Preslav, were subjected to cluster and discriminant analysis. The local origin of part of the analysed samples was proven and some conclusions about the technology of production were possible.     

ROMAN AND MEDIEVAL GLASS FROM THE ITALIAN AREA: BULK CHARACTERIZATION AND RELATIONSHIPS WITH PRODUCTION TECHNOLOGIES*

Compositional investigations were performed on 81 Roman and medieval glass fragments (first to 14th centuries ad ) from four Italian archaeological sites. The samples were soda–lime–silica in composition, with natron as flux for the Roman and early medieval glass samples, and with plant ash as flux for the late medieval ones. The varying colours are due to the differing FeO, Fe ₂ O ₃ , MnO and Sb ₂ O ₃ contents. Hierarchical cluster analysis identified six compositional groups related to age, which were compared with those found in the literature. In this way, technological continuity from the Roman to the early medieval period and the appearance of plant ash technology in the ninth century, 200 years in advance of the period previously believed, are demonstrated.     

COMPLEMENTARY COMPOSITIONAL ANALYSIS OF FORMATIVE PERIOD CERAMICS FROM THE TEOTIHUACAN VALLEY

During the Classic Period, Teotihuacan was an economic centre of central Mexico, but little is known about the development of this system. This paper presents a pilot study in multi‐method analysis of Formative Period (1500/1400 bc –ad 150) ceramics from the Teotihuacan Valley. Pottery was characterized by instrumental neutron activation analysis, laser ablation inductively coupled plasma mass spectrometry, thermal ionization mass spectrometry and petrography. It appears that most pottery was made from local raw materials that differ from later Postclassic materials. Some inter‐village interaction is suggested by stylistic choices, and one settlement had a group of ceramics made from unequivocally distinct raw materials. The study demonstrates how complementary methods can be used to draw greater anthropological meaning from compositional differences.     

CHEMICAL AND MINERALOGICAL CHARACTERIZATION OF SASANIAN AND EARLY ISLAMIC GLAZED CERAMICS FROM THE DEH LURAN PLAIN,SOUTHWESTERN IRAN*

One hundred and seventy‐five glazed ceramics from Sasanian and Early Islamic period sites located on the Deh Luran Plain in southwestern Iran were examined by instrumental neutron activation analysis for characterizing differences in ceramic pastes and by laser‐ablation inductively coupled plasma mass‐spectrometry for identifying the constituents of the ceramic glazes. The results of the analysis reveal that alkaline‐based glazed ceramics have paste compositions that are distinct from contemporary and later ceramics decorated with alkaline–low‐lead and lead‐based glazes.     

STAINING OF ARCHAEOLOGICAL GLASS FROM MANGANESE‐RICH ENVIRONMENTS*

It has been suggested that both internal and external sources of manganese may produce the black or brown staining that often occurs in buried archaeological glass. Modern potash glass of a manganese‐free medieval composition was scratched, etched and immersed in an aqueous solution containing dissolved manganese. After several weeks, immersion samples were sectioned and examined by SEM–EDX. Manganese was shown to be present in fissures and cracks within in the glass, where alkali had been depleted. Manganese from an external source is capable of blackening buried medieval potash glass.     

LATE ROMAN GLASS FROM THE ‘GREAT TEMPLE’ AT PETRA AND KHIRBET ET‐TANNUR,JORDAN—TECHNOLOGY AND PROVENANCE

Forty‐seven window and vessel glasses from the ‘Great Temple’ at Petra (Jordan), dating to the first/second and fourth centuries ce , were analysed by EPMA for major and minor elements. A subset of 29 samples from Petra and 15 samples from Khirbet et‐Tannur were additionally analysed for trace elements, using LA–ICP–MS. Six compositional groups were identified on the basis of the presence of decolouring agents. The majority of the glasses derive ultimately from the Levantine coast, but most of the groups show evidence for highly selective recycling. The observed differences between the two sites could be related to different chronological ranges, functions, relative wealth and trade connections.     

THE PROVENANCE OF OBSIDIAN ARTEFACTS FROM THE WĀDĪ ATH‐THAYYILAH 3 NEOLITHIC SITE (EASTERN YEMEN PLATEAU) BY LA–ICP–MS

The geological sources of obsidian in the Red Sea region provide the raw material used for the production of obsidian artefacts found in prehistoric sites on both sides of the Red Sea, as far afield as Egypt, the Persian Gulf and Mesopotamia. This paper presents the chemical characterization of five obsidian geological samples and 20 prehistoric artefacts from a systematically excavated Neolithic settlement in highland Yemen. The major element concentrations were determined by SEM–EDS analysis and the trace element concentrations were analysed by the LA–ICP–MS method, an almost non‐destructive technique capable of chemically characterizing the volcanic glass. A comparison of archaeological and geological determinations allows the provenance of the obsidian used for the Neolithic artefacts to be traced to definite sources in the volcanic district of the central Yemen Plateau.     

NEUTRON ACTIVATION ANALYSIS OF AD 1660–1930 EUROPEAN COPPER-COLOURED BLUE GLASS TRADE BEADS FROM ONTARIO,CANADA

Blue glass trade beads from well-dated late seventeenth- to early twentieth-century sites and collections have been analysed non-destructively by instrumental neutron activation analysis. The beads display enough variations in their elemental contents to allow us to characterize the different chemistries. The implication of these results is that similar chemical analyses of blue beads from undated archaeological sites may be used to help date the sites, since each bead chemistry has a specific earliest period.     

CHALLENGES IN THE ANALYSIS OF HETEROGENEOUS POTTERY BY LA–ICP–MS: A COMPARISON WITH INAA*

Tempers added to pottery have the potential to obscure geographical variation in the chemistry of exploited clay resources when analysed using bulk methods. A pilot study was conducted to assess the possibility of using LA–ICP–MS to analyse clay matrix in pottery with extremely subtle partitions between INAA chemical groups. LA–ICP–MS was used to analyse the clay matrix of 32 pottery samples from seven Middle and Late Woodland period (c. ad 200–800) sites in north‐east Florida and results were compared to data from INAA of the same samples. The results reveal many of the challenges in analysing highly heterogeneous materials with LA–ICP–MS. However, the study also generated data that are potentially useful in the determination of pottery provenance. In some respects, LA–ICP–MS of clay matrix replicated the chemical variation recorded by INAA, and in other respects the results are divergent. The similarities and differences between these results are explained by specific differences between the methods and the materials analysed (matrix versus bulk analysis). Suggestions for improving the method are discussed.     

CHEMICAL ANALYSES OF GLASS BEADS FOUND IN TWO SARMATIAN BURIALS*

The chemical compositions of 14 glass beads from two Early Sarmatian-period burials were determined. Al, Ca, Fe, Mg, K, Na, and Si were measured by electron probe microbeam analysis, while the Co, Cu, Ga, Mn, Ni, Pb, Rb, Sr, Th, Ti, Y, Zn, and Zr contents were measured using energy dispersive X-ray fluorescence. All the beads can be classed as low-magnesia soda-lime-silica glasses. The blue glass beads examined in this study were coloured with Co and Cu containing minerals. Cluster analysis and principal components analysis suggest that two distinct glass recipes were used to manufacture these beads.     

COLOUR ATTRIBUTES OF MEDIEVAL WINDOW PANES: ELECTRON PARAMAGNETIC RESONANCE AND PROBE MICROANALYSES ON STAINED GLASS WINDOWS FROM PAVIA CARTHUSIAN MONASTERY*

Stained glass windows from the Carthusian Monastery of Pavia, dating back to the 15th century, were studied by combining two analytical techniques: electron probe micro‐analysis (EPMA) and electron paramagnetic resonance (EPR). Chemical compositions and oxidation states of the transition ions, present as minor elements, were investigated by EPMA and EPR, respectively, in order to ascertain the role played by chromophorous ions in the glass coloration. The investigated glass can be defined as K–Ca glass, and the panes with red, green and blue colours were produced using flashing techniques.     

DEEPLY COLOURED AND BLACK GLASS IN THE NORTHERN PROVINCES OF THE ROMAN EMPIRE: DIFFERENCES AND SIMILARITIES IN CHEMICAL COMPOSITION BEFORE AND AFTER ad 150*

In this work we attempt to elucidate the chronological and geographical origin of deeply coloured and black glass dating between 100 bc and ad 300 on the basis of their major and trace element compositions. Samples from the western and eastern parts of the Roman Empire were analysed. Analytical data were obtained by means of a scanning electron microscope – energy‐dispersive system (SEM–EDS, 63 samples analysed) and laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS, 41 samples analysed). Among the glass fragments analysed, dark brown, dark purple and dark green hues could be distinguished. Only among the dark green fragments could a clear compositional distinction be observed between fragments dated to the periods before and after ad 150. In the early samples (first century bc to first century ad ), iron, responsible for the green hue, was introduced by using impure sand containing relatively high amounts of Ti. In contrast, a Ti‐poor source of iron was employed, containing Sb, Co and Pb in trace quantities, in order to obtain the dark green colour in the later glass samples. The analytical results obtained by combining SEM–EDS and LA–ICP–MS are therefore consistent with a differentiation of glassmaking recipes, detectable in glass composition, occurring in the period around ad 150.     

COMPOSITION PROFILES AND TIME EVOLUTION OF BURIED MARBLE PATINAS BY LA–ICP–MS AND LASER‐INDUCED MICRO‐PHOTO‐LUMINESCENCE

The present work aims to study surface composition profiles on buried marbles as well as their time evolution. Fifty samples from gravestones, buried for up to 80 years, were analysed by laser‐induced photoluminescence and LA–ICP–MS. The results include profiles of ²⁵Mg, ²⁷Al, ⁵⁵Mn, ⁵⁷Fe, ⁸⁸Sr and organic complexes of calcium, existing in the marble patina. The depth at which ⁸⁸Sr reaches its bulk value proved to be the best parameter to measure patina thickness. A diffusion model adopted from dissolution studies made on gravestones exposed to the atmosphere was successfully applied to the patina thickness data. The model fails to predict patina thicknesses for ancient excavated objects. However, it seems that ‘Sr alteration depth’ values alone can be used for discriminating ancient from recently buried surfaces.     

STUDY ON THE PROVENANCE OF XICUN QINGBAI WARES FROM THE NORTHERN SONG DYNASTY OF CHINA

The Xicun kiln in Guangdong Province was a famous porcelain kiln in the Song Dynasty of China, and for years there has been controversy over the provenance of Xixun Qingbai wares. This paper analyses Qingbai samples from the Xicun, Hutian (Jingdezhen) and Chaozhou (Guangdong Province) kilns by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and energy‐dispersive X‐ray fluorescence probe (EDXRF). The analytical results indicate that wares with a thin body excavated from the Xicun kiln site were produced in the Hutian kiln, and wares with a thick body were locally fired in Xicun; the contents of trace elements (V, Rb, Ba, Ta, Pb and Th) and the Nb/Ta ratio can be used to discriminate the products from the Xicun and Chaozhou kilns.     

NEUTRON ACTIVATION ANALYSIS OF SIXTEENTH- AND SEVENTEENTH-CENTURY EUROPEAN BLUE GLASS TRADE BEADS FROM THE EASTERN GREAT LAKES AREA OF NORTH AMERICA*

Sixteenth- and seventeenth-century European blue glass trade beads from aboriginal sites in the eastern Great Lakes area of North America have been analysed non-destructively using low neutron dose instrumental neutron activation analysis, so that the beads could be returned to their keepers. Dark blue (cobalt-coloured) beads are readily separable from turquoise (copper-coloured) beads. Differences in the chemistries of the turquoise blue beads appear to be useful in separating glass beads from the two centuries. Low calcium, sixteenth-century turquoise beads tend to distintegrate by a leaching of the alkali metals.