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.     

The use of oxygen,strontium and lead isotopes to provenance ancient glasses in the Middle East

It is sometimes possible to discriminate between glasses made at different factory sites by using chemical analysis. However, this is not necessarily a means of provenancing them unambiguously because glass of slightly different compositions may have been fused using different proportions of the same raw materials. The determination of oxygen, strontium and lead isotopes can provide the possibility of linking the geological sources of the glass raw materials to the production sites on which the glass was fused. Here we consider the possible isotope contributions made to the raw materials thought to have been used in the manufacture of plant ash and natron glasses found at 8th–9th century al-Raqqa, Syria. The isotopic data from al-Raqqa are compared with published results from other Middle Eastern and German glasses. We show that strontium isotopes, in particular, provide a reliable means of distinguishing between the sources of plant ash glass raw materials and that oxygen and lead isotope signatures are less discriminatory.     

A geochemical study of Roman to early Byzantine Glass from Sagalassos,South-west Turkey

The finding of glass chunks together with fuel ash slag and kiln fragments related to glass processing strongly suggests local secondary production (working) of glass at Sagalassos (SW Turkey) from imperial to early Byzantine times. Chemical evidence shows that different silica raw materials were used in imperial and early Byzantine times for blue and green glass found locally. Colourless glass shows no clear difference in chemical composition and hence in silica raw materials between late Roman and early Byzantine times. Locally found early Byzantine yellow-green glass and chunks correspond to the previously defined Byzantine HIMT glass type. The chemical composition of the glass chunks found, identical to that of the contemporary glass of the same colour, strongly indicates that these chunks were used for the manufacture of early Byzantine green, colourless and yellow-green glass at Sagalassos.The homogenous lead isotopic composition of the chronological groups of blue glass, suggests the use of two distinct but homogenous silica raw materials for the manufacture of this glass. In view of this homogeneity, it is likely that contemporary blue glass was produced at a single location. The linear trend of the heterogeneous lead isotopic composition of the green and colourless glass is a strong indication of recycling effects in the glass composition. The end members of this trend are formed by the isotopic composition of the blue glass on the one hand, and of the yellow-green (HIMT) glass on the other hand. The heterogeneous lead isotopic composition of the yellow-green glass at Sagalassos is probably the result of recycling of this glass, reflecting mixtures of the original lead isotopic signatures of the broken glass and the original HIMT glass chunks.It should be noted that the two main raw materials for primary glass production (silica and soda) were available on the territory of Sagalassos. Moreover, the lead isotopic composition of quartz pebbles sampled from the artisanal quarter of Sagalassos, is similar to that of the local blue glass.     

Analyses of colourless Roman glass from Binchester,County Durham

Forty samples of Roman colourless glass tableware from Binchester, dating from the 1st to mid-3rd centuries AD, were analysed using ICP spectrometry and parallels were sought with similar studies of Roman glass from Colchester and Lincoln [C. Mortimer, M.J. Baxter, Analysis of Samples of Colourless Roman Vessel Glass from Lincoln, Ancient Monuments Laboratory Report 44/1996, 1996; H.E.M. Cool, J. Price, Roman vessel glass from excavations in Colchester, 1971–1985, Colchester Archaeological Report 8, Colchester Archaeological Trust Ltd. and English Heritage, Colchester, 1995; M.P. Heyworth, M.J. Baxter, H. Cool, Compositional Analysis of Roman Glass from Colchester Essex, Ancient Monuments Laboratory Report 53/1990, 1990]. Some samples from the Binchester, Colchester and Lincoln (BCL) groups were re-analysed using energy dispersive spectrometry (SEM–EDS) and the results were used to compensate for the differences in reproducibility between the ICP data sets, so that these could be directly compared. The majority of the glass from all three sites was similar but some distinct compositional characteristics were identified that were specific to certain types of ware. There were differences in the concentration of lead in the samples, which appear to be to some extent chronological. The compositional data for the glass from Binchester, Colchester and Lincoln were also compared to literature data for various types of natron glass produced in the 1st millennium AD.     

青海大通县出土汉代玻璃的研究

本文共对12件玻璃样品进行化学组成分析.其中,部分样品还进行了密度测定,X 射线衍射分析和显微镜观察.此外,还对一颗黄色玻璃珠的表面层进行 SEM-EDX 分析.结果表明,该玻璃珠表面有金箔涂层.根据分析结果,青海大通县出土玻璃的基础成分可归为三类,即铅钡玻璃(Na_2O-PbO-BaO-SiO_2系统玻璃),钠钙玻璃和钾硅玻璃(K_2O-SiO_2系统)。此外,还对玻璃的来源进行了探讨.     

海昏侯墓出土马蹄金、麟趾金内嵌物的分析研究

南昌西汉海昏侯墓发掘出土了数量较多的马蹄金,为汉代黄金货币的研究工作提供了宝贵资料,出土马蹄金内均存在镶嵌物,大部分腐蚀严重。结合偏光显微分析、背散射扫描电镜\能谱、红外光谱、X射线衍射光谱对海昏侯墓主棺头箱出土的部分马蹄金内嵌物进行分析研究,依据分析结果将马蹄金内嵌物分为透闪石软玉、蛋白石、铅钡玻璃和疑似高铅玻璃4种类型。其中,铅钡玻璃基本保留玻璃态,腐蚀产物随着埋藏环境的变化存在二次结晶现象,腐蚀的最终产物是碳酸铅;疑似高铅玻璃表现出完全不同的腐蚀状态,外层硅质成分较高形成较为致密的壳状结构,内部碳酸铅以葡萄状填充在少量的硅质成分中。研究结果可为后续的保护处理与马蹄金、麟趾金的复制工作提供理论支持。     

On technology and production techniques of early medieval glass rings from Silesia

Glass rings used to be one of the most common jewellery types in the 10th–13th centuries in Central Europe, especially Silesia. The popularity of this type of decoration in this area could indicate its local origin. The chemical composition of the glass seems to confirm this theory. The Silesian glass rings analysed in this paper were made of high‐lead alkaline and non‐alkaline glass or of lead‐ash glass. There was also a close relationship between the colour of the finished products and the chemical composition of the glass. This provides new data for the study of the problem of production and distribution of glass jewellery in Central Europe.     

Glass from the Archaeological Museum of Adria (North-East Italy): new insights into Early Roman production technologies

In the present study, the first archaeometric data on an ample selection of intentionally coloured (or decoloured) Early Roman glass (1st–2nd centuries AD) from the Archaeological Museum of Adria (Rovigo, Italy) are reported. The analysed samples are 61 in total, both transparent and opaque, and were characterised from the textural (SEM-EDS), mineralogical (XRPD) and chemical (XRF, EPMA, LA-ICP-MS) points of view. This combined approach allowed us to identify the raw materials and production technologies employed in the manufacture of glassware. Results for the transparent samples show that they are all silica-soda-lime glasses. Most of them, independently of colour, have compositions close to those of typical Roman glass, produced with natron as flux. No relationships were identified among chemical compositions, types or production techniques, but a dependence on bulk composition was identified for some particular colours, revealing the careful and intentional selection of raw materials. This is the case of Sb-colourless glass, produced with sand of high purity, a group of intensely coloured objects, mainly emerald green and black, produced with soda ash as flux, and some blue examples produced with various sources of sand or soda ash as flux. Two main types of opacifiers were identified for the opaque samples: calcium antimonate for white, mauve and blue glasses, and lead antimonate for the yellow ones; in one case, a yellow lead-tin antimonate was also identified. As regards the opaque glasses, most of the samples opacified with calcium antimonate are silica-soda-lime in composition, similar to the typical Roman glass. Instead, samples opacified with lead and/or lead-tin antimonates are lead glasses, suggesting different production technologies.     

COMPOSITIONAL VARIATION IN ROMAN COLOURLESS GLASS OBJECTS FROM THE BOCHOLTZ BURIAL (THE NETHERLANDS)*

We investigated the major and trace element composition and Pb and Sr isotope characteristics of a series of about 20 colourless glass objects from a single high‐status Roman burial from the Netherlands (Bocholtz). The major elements show a relatively homogeneous group, with one outlier. This is corroborated by the Sr isotopes. Based on the Sb and Pb content, three major groups can be discerned, with two other outliers. This grouping is corroborated by the contents of the trace elements Bi, Sn, Ag, As and Mo, and by variations in lead isotopic ratios. On the basis of these results, we conclude that the glass of all objects was probably made with sand and lime from the same source. The variation in trace elements and lead isotope composition is most likely the result of variations in the composition of the sulphidic antimony ore(s) that were used to decolourize the glass. The composition of the Bocholtz glass is compared with that of other Roman glass, and implications for production models, trade and use of colourless glass objects are discussed. On the basis of isotopic and major element variation, we conclude that the antimony ore presumably originated from different mines.     

LEAD ISOTOPIC ANALYSIS OF EIGHTEENTH‐DYNASTY EGYPTIAN EYEPAINTS AND LEAD ANTIMONATE COLOURANTS*

New lead isotopic analyses are presented for lead antimonate coloured glass and faience from Amarna in Middle Egypt and dated to around 1350 BC. When compared to existing data, these suggest that Gebel Zeit on the Red Sea coast of Egypt may be the source for some of the lead antimonate colourants used in Egypt and possibly for the galena kohls of Eighteenth‐Dynasty date as well.     

MEDIEVAL GLASS FROM ROCCA DI ASOLO (NORTHERN ITALY): AN ARCHAEOMETRIC STUDY

An archaeometric study was performed on 33 medieval glass samples from Rocca di Asolo (northern Italy), in order to study the raw materials employed in their production, identify analogies with medieval glass from the Mediterranean area and possible relationships between chemical composition and type and/or production technique, contextualize the various phases of the site and extend data on Italian medieval glass. The samples are soda–lime–silica in composition, with natron as flux for early medieval glasses and soda ash for the high and late medieval ones. Compositional groups were identified, consistent with the major compositional groups identified in the western Mediterranean during the first millennium AD . In particular, Asolo natron glass is consistent with the HIMT group and recycled Roman glass; soda ash glass was produced with the same type of flux (Levantine ash) but a different silica source (siliceous pebbles, and more or less pure sand). Cobalt was the colouring agent used to obtain blue glass; analytical data indicate that at least two different sources of Co were exploited during the late medieval period. Some data, analytical and historical, suggest a Venetian provenance for the high/late medieval glass and a relationship between type of object (beaker or bottle) and chemical composition.     

The Production of Lead–Tin Yellow at Merovingian Schleitheim (Switzerland)*

A Merovingian crucible fragment, with internally adhering yellow glass, and yellow glass beads of the same region and period were investigated by non‐destructive XRF, optical microscopy and SEM‐EDS. Although the microstructure and chemical composition of the yellow pigment (lead–tin yellow type II, ‘PbSnO₃’) are almost identical in both the beads and the crucible, in the latter the pigment occurs in a much higher concentration. However, the glass base in the beads and the crucible is very different, indicating that the beads were not manufactured directly from the crucible. Instead, the crucible most likely served to produce lead–tin yellow, which was subsequently mixed elsewhere with a colourless soda–lime glass to produce yellow glass beads.     

Degradation processes in colourless Roman glass: cases from the Bocholtz burial

A group of Roman glass objects from the Bocholtz burial in the SW of Limburg (The Netherlands) was found to have been subject to varying degrees of degradation. Many of the 25 colourless glass objects were fragmented to pieces <0.1 cm (“sugared”), whereas the three transparent blue-green glass objects were in near-pristine state. Analyses using SEM, XRF and EDS revealed that the fragmentation was the direct result of the intense leaching of Na₂O from the glass structure and its replacement with water. The resulting gel layers with low-Na₂O contents and large amounts of water are sensitive to cracking when they dry out. Thin-walled glass appears to be less sensitive to cracking from the resulting stress than thick-walled glass. Local differences in the moisture regime during burial also influence the severity of the glass degradation. Glass with low concentrations of CaO seems to be the most sensitive to this form of degradation. The typical blue-green Roman glass is less sensitive as it generally has considerably higher concentrations of CaO.     

Evidence for glass ‘recycling’ using Pb and Sr isotopic ratios and Sr-mixing lines: the case of early Byzantine Sagalassos

The secondary production (working) of glass from imperial to early Byzantine times has been proven at the ancient city of Sagalassos (SW Turkey) by the existence of glass chunks, fuel ash slag and kiln fragments related to glass processing. It had been previously suggested that local green glass might have been recycled from two other locally found glass types (blue glass vessels and chunks and HIMT glass chunks). This paper provides analytical evidence for the recycling of glass next to the use of imported raw glass. The heterogeneous lead isotopic composition of the green and HIMT vessel glass at Sagalassos, with as end members on the one hand the isotopic composition of local blue glass vessels and chunks and on the other hand that of the HIMT glass chunks, could indicate the production of ‘recycled’ glass, although heterogeneous raw materials could have been used. However, the use of Sr-mixing lines confirms local recycling. It is clear that the Sr in the green and HIMT vessels is a mixture of the Sr in the aforementioned end members. It cannot be proved whether the green ‘recycled’ glass was produced from a mixture of chunks alone, or from a mixture of cullet and chunks. Suggestions are made towards the possible origin of the raw materials for the blue and HIMT glass on the basis of Sr isotopic signatures and absolute Sr contents in the glass.     

Glass Fragments from the Crypta Balbi in Rome: the Composition of Eighth‐century Fragments

Eighth‐century glass fragments from the Crypta Balbi in Rome were analysed by inductively coupled plasma emission spectroscopy. The samples included fragments of artefacts as well as ingots of raw glass and wasters. All the fragments proved to be soda–lime glasses. Manganese‐to‐iron atomic ratios are highly variable and determine the colour of a large number of samples. Fairly high copper contents, generally associated with relatively high amounts of antimony and lead, were detected in some green and blue–green samples: this suggests recycling of glass in the form of opaque mosaic tesserae. All three elements are higher in eighth‐century than in previously analysed seventh‐century fragments. This may indicate greater recourse to recycled glass, related to a reduction in trade exchanges in the Mediterranean.     

Identification of PbO (BaO) faience from an early and middle Warring States period cemetery at Zhaitouhe,northern Shaanxi,China

Low‐temperature vitreous materials fluxed with lead (and barium) appeared in the early Warring States period (c.fifth century bce ) in ancient China. A range of lead vitreous products fluxed with the same agent, including faience/glass beads, glazed pottery and Chinese blue (purple) pigment, were developed subsequently. This study carries out scientific analysis of six vitreous beads unearthed from the Zhaitouhe cemetery site in northern Shaanxi dating to the early and middle Warring States period to investigate their chemical composition, microstructure and coloration. The lead (and barium) vitreous beads identified here are some of the earliest lead vitreous materials discovered in China so far, and therefore important for the study of the development of lead vitreous technologies in ancient China. This paper also points out that it is meaningful to evaluate the lead glass, glazed pottery and barium copper silicate pigments as a whole technological assemblage given their close relationships.     

APPLICATION OF LEAD ISOTOPE ANALYSIS TO A WIDE RANGE OF LATE BRONZE AGE EGYPTIAN MATERIALS*

Lead isotope analysis was applied to Egyptian materials from the Late Bronze Age in order to investigate the relationship between these different materials, many of which have lead as a significant component. The galena kohls analysed can be provenanced to Gebel Zeit, a large mining site known to have been active during the period. However, the source of lead metal is different and seems to be outside Egypt, along with the source of copper. Lead‐based pigments such as lead antimonate that were used in glass and glazes seem mostly to come from Egypt, although they may well contain a component of ‘Mesopotamian’ lead. In the Predynastic period, galena from many sources is being exploited for use as kohl. However, by the Middle Kingdom (2055–1650 bc ), extraction has concentrated on one source, Gebel Zeit, perhaps reflecting increasingly centralized control and/or the use of large‐scale exploitation. It therefore appears that a complex pattern of trade in lead‐based materials was evident, with lead metal and galena being separate commodities from separate sources and treated as such.     

Glass Beads from 15th–17th Century CE Jar Burial Sites in Cambodia's Cardamom Mountains

A total of 74 glass beads, included as grave goods in 15th–17th century CE jar burials from Cambodia's Cardamom Mountains, were analysed using laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS). Several glass types were identified, including two subtypes of high‐alumina mineral soda glass, and lead–potash glass. The final glass type represents a newly discovered and previously unidentified type of high‐alumina soda glass, with high magnesia (m‐Na–Al Mg>). This study represents the first glass data from the mid‐second millennium CE from Cambodia and sheds light on the multiple long‐distance maritime exchange networks in which the upland people buried in the jars were participating.     

Studying the process of enamel powder preparation for émail champlevé by colour measurements and μ‐X‐ray mappings

Colour measurements and non‐destructive μ‐X‐ray mappings have been used for the first time in a comprehensive study of medieval émail champlevé works from different production areas in France and Germany. This approach has given a new insight into the enamel powder preparation process of the glass material used for enamelling. Colour measurements demonstrated that all production centres used glass of very similar hues, but with large differences in colour saturation. The μ‐X‐ray mapping results of blue enamels are described by a semi‐qualitative approach. Significant variations in oxide contents of lead, cobalt, manganese and antimony oxides were found. The variations suggest that more than one glass material was used to prepare the powder for enamelling. The variations in antimony and cobalt show that glass had different degrees of opacity and colour depth. The manganese and lead contents, which do not correlate with the cobalt or antimony contents, indicate that probably glass of different base compositions was used to prepare the enamel powder for one champlevé field.