A non-invasive study of Roman Age mosaic glass tesserae by means of Raman spectroscopy

Ancient mosaic tesserae are a range of materials of very varied and complex nature, including pottery, stone and glass. Raman spectroscopy is a powerful tool for the analysis of all these kinds of materials. In the particular case of glasses, this technique can be used both for a study of surface weathering and for the characterization of bulk structure, but it has not yet been extensively used for the characterization of mosaic glass tesserae. We carried out Raman analyses on a set of Roman and Late Antiquity period mosaic glass samples, which allowed a good characterization of both the glass matrix and the crystalline inclusions. All the samples show the typical Raman signatures of soda-lime-silicate glasses. Several crystalline phases were also identified, being relics of raw materials used during the glass manufacturing process, such as quartz and feldspars, or linked to the glass color/opacification, such as bindheimite and cuprite. The analyses also led to the identification in some blue, turquoise and green tesserae of calcium antimonate, whose Raman signature has only recently been recognized in the scientific literature on mosaic glasses. Some emphasis is given to the analysis of red lead-containing tesserae, colored with Cu⁺ ions or even Cu⁰ (or Au⁰) metal nanoparticles. Samples with peculiar compositions, as well as “modern” (and restoration) samples, could quite easily be distinguished from the ancient ones by their Raman spectra.     

FURTHER STUDIES IN THE COMPOSITIONAL VARIABILITY OF COLOURLESS ROMANO‐BRITISH VESSEL GLASS*

Previous studies of colourless Romano‐British vessel glasses have suggested that, regardless of vessel type, they show considerable compositional homogeneity. Intriguing differences in variability (as opposed to mean composition) have, however, also emerged. This paper reports on a compositional study of 243 vessels, that is larger and more carefully controlled than in previous studies of this kind. Unexpected compositional differences have been found both between and within the four vessel types studied. We discuss the implications of these results in the context of different models that have been proposed for glass‐making and glass‐working in the Roman world.     

A NEW DATING METHOD FOR HIGH‐CALCIUM ARCHAEOLOGICAL GLASSES BASED UPON SURFACE‐WATER DIFFUSION: PRELIMINARY CALIBRATIONS AND PROCEDURES*

The first European settlers came to North America in the early 17th century using glass in the form of containers and decorative objects. Thus, glass is a horizon marker for all historic period settlements and a potential source of chronometric dates at archaeological sites belonging to the historic period in the Americas. We have developed a new absolute dating method based upon water diffusion into the surface of manufactured glasses that predicts diffusion coefficients based upon variation in glass chemical constituents. Low‐temperature (< 190°C) hydration experiments have been performed on a set of five high‐calcium (21.7–28.3%) glasses that were used to manufacture wine bottles from the 17th?19th centuries. Infrared spectroscopy and secondary ion mass spectrometry was used to model the water diffusion/alkali exchange process. The ability of the model to accurately predict archaeological ages was evaluated with artefacts recovered from ceramic‐dated contexts at Thomas Jefferson's plantation known as Monticello.     

RAW MATERIALS OF GLASS FROM AMARNA AND IMPLICATIONS FOR THE ORIGINS OF EGYPTIAN GLASS*

Analysis has been conducted on 19 blue glasses from Amarna in Middle Egypt dated to around 1350 BC. The results suggest that these glasses fall into two distinct types: cobalt coloured glasses with a natron based alkali made from local Egyptian materials, and copper coloured glasses with a plant ash alkali, which follow a Mesopotamian tradition of glass making. It is suggested that at least some of this copper/plant ash glass is imported into Egypt during the Amarna period despite extensive local production of cobalt/natron glass. Existing analyses (Lilyquist and Brill 1995) of the earliest glass from the reign of Tuthmosis III (c. 1450 BC) suggest that during this period the same two types of glass are present. Local Egyptian cobalt and natron in these early glasses implies that, despite the lack of archaeological evidence for production sites, glass was produced from its raw materials in Egypt as early as the reign of Tuthmosis III.     

X-RAY MICROANALYSIS OF ANCIENT GLASSY MATERIALS: A COMPARATIVE STUDY OF WAVELENGTH DISPERSIVE AND ENERGY DISPERSIVE TECHNIQUES*

Sensitivity, precision and accuracy of quantitative microanalysis of major, minor and trace elements present in ancient glasses by energy dispersive spectrometry (EDS) is compared to that by wavelength dispersive spectrometry (WDS). Although there are certain problems with EDS due to peak overlaps and background noise, the precision and minimum detection limits of EDS for most of the important elements in ancient glasses were found to compare favourably to those of WDS. Both EDS and WDS, when quantified by comparison to glass standards, can produce reliable results which are adequate for most technological questions.     

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.     

DISCOVERY,PRODUCTION AND USE OF TIN‐BASED OPACIFIERS IN GLASSES,ENAMELS AND GLAZES FROM THE LATE IRON AGE ONWARDS: A REASSESSMENT*

Tin‐based opacifiers (lead stannate yellow and tin oxide white) were first used in glass production for a short period in Europe from the second to the first centuries bc , and then again throughout the Roman and Byzantine Empires from the fourth century ad onwards. Tin oxide was also used in the production of Islamic opaque glazes from the ninth century ad , and subsequently in enamels applied to Islamic and Venetian glasses from the 12th century ad onwards. A selection of published analytical data for the tin‐opacified glasses, enamels and glazes is summarized, and the methods used in their production are reassessed. The phase transformations occurring when mixtures of lead oxide, tin oxide and silica are fired are investigated with high temperature X‐ray diffraction (XRD) using a synchrotron radiation source, and these results are used to explain the observed differences in the glass, enamel and glaze compositions. Possible reasons for the use of tin‐based opacifiers in the second to first centuries bc , and for the switch from antimony‐ to tin‐based opacifiers in the fourth century ad are suggested, and the possible contexts in which tin‐based opacifiers might have been discovered are considered. The introduction of tin‐opacified glazes by Islamic potters in the ninth century ad is discussed in terms of technological transfer or independent invention.     

ELECTRON PROBE MICROANALYSIS OF MIXED-ALKALI GLASSES

European mixed-alkali glasses are compared with Sayre and Smith's categorisation for ancient glass and with the chemical compositions of other prehistoric and later European glasses. The new categories reported here indicate that a wide range of alkali raw materials was used in the production of glasses found in prehistoric European contexts. At least five major chemical categories of glass are now known to have been used in prehistoric and early Roman Europe. A plant species of the genus Sulicorniu is suggested as a possible alkali source in ancient European glasses.     

Radical changes in Islamic glass technology: evidence for conservatism and experimentation with new glass recipes from early and middle Islamic Raqqa,Syria*

The chemical analysis of excavated glass fragments from dated archaeological contexts in Raqqa, Syria, has provided a detailed picture of the chemical compositions of artefacts deriving from eighth to ninth and 11th century glassmaking and glassworking activities. Evidence for primary glass production has been found at three excavated sites, of eighth to ninth, 11th and 12th century dates; the first two are discussed here. The 2 km long industrial complex at al‐Raqqa was associated with an urban landscape consisting of two Islamic cities (al‐Raqqa and al‐Rafika) and a series of palace complexes. The glass fused and worked there was presumably for local as well as for regional consumption. Al‐Raqqa currently appears to have produced the earliest well‐dated production on record in the Middle East of an Islamic high‐magnesia glass based on an alkaline plant ash flux and quartz. An eighth to ninth century late ‘Roman’/Byzantine soda–lime recipe of natron and sand begins to be replaced in the eighth to ninth century by a plant ash – quartz Islamic soda–lime composition. By the 11th century, this process was nearly complete. The early Islamic natron glass compositional group from al‐Raqqa shows very little spread in values, indicating a repeatedly well‐controlled process with the use of chemically homogeneous raw materials. A compositionally more diffuse range of eighth to ninth century plant ash glass compositions have been identified. One is not only distinct from established groups of plant ash and natron glasses, but is believed to be the result of experimentation with new raw material combinations. Compositional analysis of primary production waste including furnace glass (raw glass adhering to furnace brick) shows that contemporary glasses of three distinct plant ash types based on various combinations of plant ash, quartz and sand were being made in al‐Raqqa during the late eighth to ninth centuries. This is a uniquely wide compositional range from an ancient glass production site, offering new insights into the complexity of Islamic glass technology at a time of change and innovation.     

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.     

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.     

SCIENTIFIC ANALYSIS OF SEVENTH‐CENTURY GLASS FRAGMENTS FROM THE CRYPTA BALBI IN ROME*

Inductively coupled plasma emission spectroscopy, reflectance spectroscopy and X‐ray diffraction were used to study seventh‐century AD glass fragments from the Crypta Balbi in Rome. All the samples were found to be silica‐soda‐lime glasses. Iron determines the colour of blue‐green, green and yellow‐green transparent glasses; chemical composition suggests deliberate addition of iron and/or manganese in about half the samples. Copper was found as the main colourant in red, pale blue and blue‐green opaque fragments; elemental copper acts as an opacifier in red glass, and calcium antimonate in white, pale blue and blue‐green glasses. Detection of antimony in transparent fragments suggests recycling of opaque mosaic tesserae.     

Strontium Isotopes in the Investigation of Early Glass Production: Byzantine and Early Islamic Glass from the Near East*

⁸⁷Sr/⁸⁶Sr ratios have been determined for glasses from four production sites, dated to between the sixth and the 11th centuries, in the Eastern Mediterranean region. On the basis of elemental analyses, the glasses at each location are believed to have been melted from different raw materials. Two glass groups, from Bet Eli‘ezer and Bet She‘an, in Israel, are believed to have been based upon mixtures of Levantine coastal sands and natron, and have ⁸⁷Sr/⁸⁶Sr ratios close to 0.7090, plus high elemental strontium, confirming a high concentration of modern marine shell (⁸⁷Sr/⁸⁶Sr ~ 0.7092) in the raw materials. The isotopic compositions of these two groups of glasses differ slightly, however, probably reflecting a varying ratio of limestone to shell because the sands that were utilized were from different coastal locations. Natron‐based glasses from a workshop at Tel el Ashmunein, Middle Egypt, have ⁸⁷Sr/⁸⁶Sr values of 0.70794–0.70798, and low elemental strontium, consistent with the use of limestone or limestone‐rich sand in the batch. High‐magnesia glasses based on plant ash, from Banias, Israel, have ⁸⁷Sr/⁸⁶Sr values of 0.70772–0.70780, probably reflecting the isotopic composition of the soils that were parental to the plants that were ashed to make the glass. Strontium and its isotopes offer an approach to identifying both the raw materials and the origins of ancient glasses, and are a potentially powerful tool in their interpretation.     

ANALYSING ARCHAEOLOGICAL BASALT USING NON‐DESTRUCTIVE ENERGY‐DISPERSIVE X‐RAY FLUORESCENCE (EDXRF): EFFECTS OF POST‐DEPOSITIONAL CHEMICAL WEATHERING AND SAMPLE SIZE ON ANALYTICAL PRECISION*

Energy‐dispersive X‐ray fluorescence (EDXRF) has been commonly used to determine geological sources of volcanic glass artefacts, but its ability to discriminate between basaltic sources is less developed. We examine the precision and accuracy of non‐destructive EDXRF for basalt artefacts by analysing varying size and weathering characteristics. The experiments identified no appreciable effect in reproducibility or measured composition due to thickness (down to 1 mm) or natural weathering of pre‐contact flake scars for the 17 elements measured in this study. Samples with surface area less than 100 mm², however, show significant variability in measured composition and reproducibility.     

THE BLUE ENAMELS IN THE BAROQUE DECORATIONS OF THE CHURCHES OF PALERMO,SICILY: FE2+‐COLOURED GLASSES FROM LIME KILNS*

Deep blue glasses coloured by octahedral Fe²⁺ cations are often reported as textbook examples of blue pigmentation. However, despite the possibility of laboratory synthesis under reducing conditions, to date there are no well‐reported occurrences of their production and use in the past. A thorough historical, ethnographic, mineralogical, and chemico‐physical investigation of the ‘smaltini di calcara’ from several baroque churches in Palermo, Sicily, has revealed that the blue enamels widely used for altar decorations in the 17th and 18th centuries are actually a unique case of ancient blue glasses pigmented by divalent iron cations in distorted octahedral coordination. This mixed‐alkali glass was accidentally produced under severely reducing conditions in the local kilns during production of lime.     

THE PROVENANCE AND TECHNOLOGY OF NEAR EASTERN GLASS: OXYGEN ISOTOPES BY LASER FLUORINATION AS A COMPLEMENT TO STRONTIUM*

The ability to make rapid measurements on small samples using laser fluorination enhances the potential of oxygen isotopes in the investigation of early inorganic materials and technologies. δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values are presented for glass from two primary production sites, four secondary production sites and a consumer site in the Near East, dating from Late Antiquity to the medieval period. δ¹⁸O is in general slightly less effective than ⁸⁷Sr/⁸⁶Sr in discriminating between sources, as the spread of measured values from a single source is somewhat broader relative to the available range. However, while ⁸⁷Sr/⁸⁶Sr is derived predominantly from either the lime‐bearing fraction of the glass‐making sand or the plant ash used as a source of alkali, δ¹⁸O derives mainly from the silica. Thus the two measurements can provide complementary information. A comparison of δ¹⁸O for late Roman – Islamic glasses made on the coast of Syria–Palestine with those of previously analysed glasses from Roman Europe suggests that the European glasses are relatively enriched in ¹⁸O. This appears to contradict the view that most Roman glass was made using Levantine sand and possible interpretations are discussed.     

CLUSTER ANALYSIS APPLIED TO SPECTROCHEMICAL DATA OF EUROPEAN MEDIAEVAL STAINED GLASSES

Cluster analysis has been applied to the spectrochemical data obtained in the analysis of some mediaeval glass fragments. Differences have been observed between Catalan glasses and all European glasses, and also between European glasses from different countries. To distinguish geographical origin sodium, potassium, calcium, magnesium and aluminium have been shown to be adequate.     

Between east and west: Glass beads from the eighth to third centuries bce from Poland

The study analyses the chemical composition of 57 glass samples from 40 beads discovered at 20 archaeological sites in Poland. The beads are dated to Hallstatt C–Early La Tène periods (c.800/750–260/250 bce ). Analyses were carried out using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Two groups were distinguished among the glasses based on the MgO/K₂O ratio: high-magnesium glass (HMG), five samples; and low-magnesium glass (LMG), 52 samples. The former were melted with halophyte plant ash, the second with mineral soda. These glasses were produced in the Eastern Mediterranean (more likely in Mesopotamia or Syro-Palestine than in Egypt) and transported in the form of semi-products to secondary glass workshops in Europe. Some of the white opaque glass was coloured and opacified in Europe.     

Isothermal Time‐Series Determination of the Rate of Diffusion of Water in Pachuca Obsidian*

Friedman and Smith's (1960) article introducing an exciting, potentially precise and inexpensive method of dating obsidian artefacts has thus far failed to reach its potential. Numerous efforts to refine, improve and even redevelop the method since that time have similarly failed to achieve the original promise. Only within the last eight years have significant improvements been made, due to both improved analytical techniques and a better understanding of the hydration process. However, most of our mechanistic understanding of the interaction of water with rhyolitic glass is based on experiments performed on melts and glasses at temperatures above their glass transitions, conditions inappropriate for investigation of near‐surface environmental conditions. Unfortunately, studies detailing the temporal evolution of the diffusion profile at low temperatures are rare, and few useful data are available on the low‐temperature diffusive hydration of silicate glasses. This paper presents data on the experimental hydration of obsidian from the Pachuca source (a.k.a. Sierra de las Navajas, Basin of Mexico) at 75°C for times ranging from 3 to 562 days, and compares these results with data for samples obtained from a stratigraphic excavation of the Chalco site in the Basin of Mexico. Samples have been analysed using secondary ion mass spectrometry (SIMS) to provide concentration/depth data. While 75°C is still significantly above the temperatures at which archaeological obsidians hydrate, it is well below the glass transition temperature (approx. 400°C) and thus processes are likely to be similar to those that occur in nature, but fast enough to be observed over a laboratory timescale. The results demonstrate that a simple square‐root‐of‐time model of the evolution of the diffusion profile is not adequate to describe the diffusion process, as measured diffusion profiles exhibit the effects of concentration‐ and time‐dependent, non‐Fickian diffusion. With progressive hydration, characteristic diffusion coefficients first decrease, then increase with time. Surface concentration increases with time, but an intermediate plateau is observed in its time evolution that is consistent with results obtained from the suite of Chalco samples. Both of these effects have been observed during diffusion in glassy polymer systems and are associated with the build‐up and relaxation of self‐stress caused by the influx of diffusing material.     

ANALYSIS OF LATE BRONZE AGE GLASS AXES FROM NIPPUR—A NEW COBALT COLOURANT

A multidisciplinary study of a unique group of Late Bronze Age (LBA) ceremonial glass axe heads and other artefacts shows that these are the first significant group of glasses coloured with cobalt to be identified from the Near East. The axes were excavated from the site of Nippur, in present‐day Iraq. Several are incised with the names of three kings, which dates the material to the 14th–13th centuries bc . Analysis by laser ablation inductively coupled plasma mass spectrometry (LA–ICPMS) indicates that the glass had high magnesia (MgO) and potash (K₂O) associated with a plant‐ash flux and was coloured blue by copper or a combination of copper and cobalt. These glasses are similar, but not identical, in major element composition to blue‐coloured glasses manufactured in ancient Egypt and elsewhere in Mesopotamia in the same period. However, the Nippur cobalt‐ and copper‐coloured glasses exhibit significantly different trace elemental compositions compared to Egyptian glass coloured with cobalt, showing that the ancient Near Eastern glassmakers had clearly identified and utilized a distinctive cobalt ore source for the colouring of this glass. Since it was previously thought that the only cobalt ores exploited in the LBA were exclusively of Egyptian origin, this new finding provides new insights on the origins of glass and how it was traded during the Bronze Age period.