THE ANALYSIS OF SECOND MILLENNIUM GLASS FROM EGYPT AND MESOPOTAMIA,PART 1: NEW WDS ANALYSES*

A recent analytical study by SEM–WDS was carried out on 226 glasses from the Late Bronze Age, analysing each of the glasses for a total of at least 22 elements, the largest such analytical study conducted on these glasses. The aim of the analysis was first to identify which elements were brought in with each of the raw materials and, second, to accurately characterize those raw materials. Since different glassmaking sites in Egypt and the Near East would probably use at least some local raw materials and these raw materials will vary slightly from site to site, this has potential for provenancing the glass. Analysis showed new patterns in the compositions of glass from the various sites and led to new conclusions about the supply of raw materials and personnel for the glass workshops. This forms the basis for further work by LA–ICPMS to be presented in part 2 of this paper.     

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。     

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.     

XRF analysis of glass beads from the Mycenaean palace of Nestor at Pylos,Peloponnesus, Greece: new insight into the LBA glass trade

In recent years there has been a growing interest in Mycenaean glass among archaeologists and scientists. Scholars have traditionally thought that all Mycenaean glass was imported either in finished form or as ingots and simply shaped or worked at the Mycenaean sites. Chemical studies of other Mycenaean glass (50 and 43) support the hypothesis that glass was imported into Mycenaean Greece, but there is also indication for glass production in mainland Greece at the palace of Thebes (Nikita and Henderson, 2006). There is no evidence for glass making or working at the Palace of Pylos, yet there is an abundance of glass beads there. The aim of this paper is to identify the technology and source for the glass of these beads and thus to ascertain how Pylos was connected to the broader Mycenaean and Mediterranean economies. The composition of the glasses was determined by means of portable XRF analysis and compared to that of other Late Bronze Age glasses from Egypt, Mesopotamia and mainland Greece. Four blue beads coloured with cobalt and one blue bead coloured with copper have Ti and Zr compositions consistent with an Egyptian origin of manufacture while five other beads show Ti and Zr concentrations consistent with a Mesopotamian origin (Shortland et al., 2007). Based on the dearth of Egyptian and Mesopotamian imports in Pylos, the presented data support the hypothesis that Pylos was receiving via internal Greek trade routes foreign-produced glass, which may have been worked abroad or in Greece.     

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.     

Sasanian glass from Veh Ardašīr: new evidences by ICP-MS analysis

Forty-seven glass fragments excavated at Veh Ardašīr, in central Iraq, were analysed by ICP-MS, determining 38 chemical elements; the samples represented finished objects as well as waste and raw glass. The obtained data point to the use of sodic plant ash for the production of glass in the entire Sasanian period (third–seventh century AD), strengthening previous results from another set of fragments from the same site. Magnesium and phosphorus contents give further evidence of the possible use of different kinds of plant ash, while trace element levels and some element correlations suggest the recourse to different silica sources. As a whole, the obtained results allow one to recognize three main glass compositions, related to the use of different silica sources combined with different kinds of plant ash. The occurrence of waste and raw glass in all groups of composition confirms that at least glass working took place in Veh Ardašīr.     

Potash - a key raw material of glass batch for Bohemian glasses from 14th-17th centuries?

The aim of this work is to verify or refute hypothesis of existence of basic/universal glass batch: quartz sand: potash: limestone, at a ratio of 2: 1: 1 used in Bohemian glass production since the middle ages onwards and to simulate the preparation of a potassium glass type with the composition used in medieval Bohemia. The chemical composition of Bohemian glass, which incorporated in the proposed glass batch for glassmaking on a laboratory scale, was evaluated by (a) findings directly related to glassmaking (samples from glasswork in Moldava dating back to the 15th century) and (b) information from publications.Experimentally produced glasses for the present paper were prepared from raw materials such as ash, leached ash, potash, limestone and quartz sand. The plant raw materials (spruce, beech and bracken ashes, raw and refined potash) were treated and prepared by methods similar to the production procedures used in the pre-industrial era.The main contrast was found in the CaO/K₂O weight ratio, which was determined in glasses that were characteristic of given periods. While this ratio was often below 1 in glasses of the 15th century, it reached values above 1 in glasses at the turn of the 16th-17th centuries. This result may indicate that the composition of the glass batch had changed.The results of the present study reject the current scholarly work dealing with glass batch composition during the 14th-17th centuries and confirm that glass produced in some Bohemian medieval glassworks could have been melted from a batch that included plant ash, making the use of limestone unnecessary. The traditional suggestion of the exact ratios of raw materials, often cited in historical literature, seems to be impossible. The glassmakers had to react to the variable composition of the raw materials, especially plant ash.     

Interpreting elements and isotopes in glass: A review

Substantial databases of elemental and isotopic analyses of ancient glass exist and are used to investigate raw material origin, trade, exchange, and processes such as mixing and recycling. However, the chemistry of archaeological glass may be challenging to the untrained. The paper provides structured information on the origin of chemical elements and their isotopes in ancient glass. It details some of the functions of individual elements in the glass and from which raw material(s) or process(es) they originate.     

The coloured glass of Iulia Felix

Research on the cargo of glass in the Roman ship Iulia Felix, wrecked off the town of Grado (province of Udine, North Italy) in the first half of the 3rd century AD and composed of recycling cullet carefully selected for colour and type, provided much information on Roman glass production technology. A combined approach, involving analytical, statistical, and archaeological evidence, included chemical analyses (X-ray fluorescence, electron microprobe), which indicated that the coloured samples were all soda-lime-silica in composition, with natron as flux, although cluster analysis identified many compositional groups. Comparisons among the compositional groups of the colourless glass, previously studied, and those of coloured glass showed that the production technologies of the colourless glass vessels constitute two well-defined technological end-members, also related to group types, into which those of the coloured glass samples fall. In particular, coloured glass samples—all bottles, low-status vessels—were produced with mainly beach siliceous-feldspar-calcareous sand. However, unlike the colourless type, strict control of raw materials and decolourising processes was not adopted, and recycling was also practised, as demonstrated by the Sb₂O₃, Cu and Pb patterns. In this context, a “recycling index” (RI)—[(Sb₂O₃)_X/(Sb₂O₃)_Ref] * 100—is proposed here for the first time, in order to quantify the extent of recycling of antimony colourless glass in the batch. RI is valid for glass containing abundant Sb from an end-member of colourless glass. In conclusion, although it cannot be stated unequivocally that the identified compositional trends are related to different production centres or different raw materials, the strong evidence of compositional variability among all the Iulia Felix glass samples, both colourless and coloured, supports the dispersed production model for Roman glassware and the common practice of recycling in Roman imperial times, especially for low-status vessels.     

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.     

Western Mediterranean sand deposits as a raw material for Roman glass production

During the Late Roman and Byzantine period, natron glass was made from its raw materials in a limited number of primary production centres in Egypt and Syro-Palestine. For the earlier Hellenistic and Roman period, no primary furnaces have been found and the location of primary production during this era remains unclear. Ancient authors such as Strabo and Pliny the Elder suggest that glassmaking sands were found near the River Belus (Israel), in Egypt, near the mouth of the Volturno River (Italy) and also in Spain and France. However, primary production in the western part of the Mediterranean is not supported by any direct archaeological evidence and possible sand raw materials from these regions have never been evaluated for their suitability to produce glass.     

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.     

The composition of late Romano-British colourless vessel glass: glass production and consumption

One hundred and twenty-eight colourless glass tablewares from settlement contexts throughout the British Isles, dating from the mid-3rd to 4th century AD, were analysed by ICP-AES spectrometry. Three distinct compositional groups were identified based upon the use of different decolourisers and primary raw materials, with possible sub-groups within these. These compositions have distinct, but overlapping chronological ranges, suggesting colourless glass production in at least three, possibly more, centres in the late Roman period. The compositional analysis highlights the high degree to which recycling of glass was taking place during this late period. The chronological distribution of some of these compositions is more restricted within the British assemblages than is observed in other published assemblages from Western Europe. This distinction may indicate different supply patterns of glass to the Western provinces.     

Glass and glass production in the Oman peninsula in antiquity reconsidered – chemical and mineralogical investigation of sands

A batch of green‐ and amber‐coloured glass chunks and unguentaria dating from the first century CE was found in 2007 at Dibba al Hisn, a site on the Arabian Sea coast of the United Arab Emirates (UAE). Its elemental and isotopic composition revealed the glass to be of a previously unknown plant ash glass type, different from known contemporary Roman, Mesopotamian, and Indian glass. The Sr isotopic composition of the glass corresponds to locally available plants, pointing to the possible existence of a first‐century CE local glass production centre. To explore this possibility, sands from around the UAE were analysed to establish their suitability for glass making and correspondence with the Dibba finds. This paper presents the results of the elemental analysis of fourteen sands. The analysis, performed using inductively coupled plasma optical emission spectroscopy (ICP‐OES), revealed all sands to be rich in lime and alumina. X‐ray diffraction revealed the presence of calcite and other carbonate minerals, as well as antigorite and quartz. Comparison of the sand compositions to average first‐century CE non‐Roman glass found at Dibba showed them to be unsuitable as raw material for producing the glass of Dibba. The evidence thus identifies this glass batch as imported, contrary to what was suggested before. This paper also reviews the occurrence of thick‐walled unguentaria in the region.     

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.     

Tracing the origins of Eastern European enamelling: Chemical composition of glass and enamels from the Bryansk hoard (south‐western Russia)

The chemical composition of a series of Eastern European enamels from the Bryansk hoard from the third century ad and other sites was studied using scanning electron microscopy with energy‐dispersive spectroscopy (SEM‐EDS) and electron microprobe analysis (EPMA) techniques. Red opaque glass is homogeneous compositionally, suggesting not only common manufacturing traditions but also identical types and sources of raw materials and, consequently, a single origin. The glass is made in the Roman tradition of enamelling, which appeared in the mid‐first century ad , as was the case with orange glass. The difference in the lead content in glass of different colours, which determines the melting temperature, allows the reconstruction of polychrome enamelling techniques.     

GLASS BY DESIGN? RAW MATERIALS,RECIPES AND COMPOSITIONAL DATA*

Compositional analyses of ancient and historic glasses have often been interpreted in terms of the use of specific raw materials in glass manufacture. However, the known inhomogeneity of many glass‐making raw materials and the insolubilities of some compounds make any explanation of compositional data problematic. This paper looks at three glass‐making alkalis with a view to understanding how the compositions of these raw materials are carried through to the final glass. The chemistry and variability of the raw materials are discussed, as is their contribution to the final glass composition. In addition, the choices and decisions made by glassmakers are acknowledged in the final glass compositions. This combination of factors addresses the complexity of predicting the use of specific raw materials from the finished glass composition.     

Archaeometric investigation of Roman tesserae from Herculaneum (Italy) by the combined use of complementary micro-destructive analytical techniques

Vitreous tesserae from two mosaics in Herculaneum (Italy) dating from the 1st century AD have been investigated in order to gather information on Imperial Age opaque glass. The combined use of complementary micro-destructive analytical techniques, namely optical microscopy (OM), scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), inductively coupled plasma-mass spectrometry (ICP-MS), transmission electron microscopy (TEM), and X-ray powder diffraction (XRPD) allowed to define the nature of formers, fluxes, chromophores and opacifying compounds and to determine the type of raw materials employed for their introduction. The results confirmed the high technological level of Imperial Age glassmakers and clarified some details of the production processes. Experimental data have been obtained concerning formation of antimony-based opacifiers. The presence of tin-containing Ca- and Pb-antimonates has been ascertained in various green, yellow and turquoise tesserae. Moreover, unusual divergences from the established Roman age ‘low magnesia–low potash’ (LMLK) glass composition have been found for some red and green samples.     

Chemical characterisation of glass mosaic tesserae from sixth-century Sagalassos (south-west Turkey): chronology and production techniques

Little is known about the origin, supply pattern and production technology of Byzantine glass mosaic tesserae. In this study, we have analysed forty-eight glass tesserae from Sagalassos (Asia Minor) of different colours and from two archaeological contexts that were stratigraphically dated to the sixth century CE. The main aim was to identify the raw materials, colourants and opacifiers as well as secondary working practices that are reflected in the composition (EPMA, LA-ICP-MS analyses) and the microstructure (XRD, SEM-BSE) of the tesserae. The set of samples retrieved from the Roman Baths complex at Sagalassos is compositionally very homogeneous, representing possibly a single commission, and can be tentatively dated to the late Roman period. In contrast, the assemblage associated with the construction of a Byzantine church around the turn of the sixth century CE is more diverse, suggesting that these tesserae were produced from more than one silica source. This highlights a diversification in the supply and manufacture of glass tesserae during the Byzantine period.     

Moving sources: A preliminary study of volcanic glass artifact distributions in northeast China using PXRF

Recent studies have highlighted the long-distance transport of obsidian from the Paektusan (Tianchi or Baitoushan in Chinese) volcano on the border between China and North Korea to eastern Russia and Korea, but little is known about the role of the local population in the production and movement or exchange of this important raw material. This paper addresses this data lacuna by presenting sourcing results of 440 artifacts from 18 Late Paleolithic sites located in northeast China. A portable XRF enabled rapid non-destructive characterization of samples. The results show that although Paektusan obsidian was widely transported throughout northeast Asia, material from at least three other sources was also used. In particular, we highlight the significance of basaltic glass artifacts with the same geochemistry as sources found in the Primorye region of Far East Russia in sites from northeast China. This result indicates a two-way movement of volcanic glass artifacts between Primorye and the northeast of China rather than a unidirectional long-distance exchange system originating from Paektusan Volcano.