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.     

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.     

A STUDY OF GLASS TESSERAE FROM MOSAICS IN THE MONASTERIES OF DAPHNI AND HOSIOS LOUKAS (GREECE)

In this work 51 glass mosaic tesserae from decorations of the two Greek monasteries of Daphni and Hosios Loukas were analysed by inductively coupled plasma optical emission spectroscopy, electron microprobe analysis and X‐ray powder diffraction. On the basis of the chemical analyses, after discrimination between the tesserae of the original decorations and those from other periods, it was possible to outline the distinctive traits of Byzantine mosaic tesserae. In both the monasteries, the original mosaics were decorated with tesserae produced with plant ash based glass, either of the typical composition or a mixture with natron type glass. The samples from the Hosios Loukas decorations show a more homogeneous composition compared with those from Daphni. The major differences among the original samples are due to the presence of opacifiers and colourants.     

Glassmaking using natron from el-Barnugi (Egypt); Pliny and the Roman glass industry

Pliny the Elder describes the discovery of a process for making natron glass, which was widely used for much of the first millennium bc and ad. His account of glassmaking with natron has since been corroborated by analyses of archaeological glass and the discovery of large-scale glass production sites where natron glass was made and then exported. Analyses of Egyptian natron have shown it to be a complex mixture of different sodium compounds, and previous experiments to make glass with Egyptian natron have been unsuccessful. Here, natron from el-Barnugi in the Egyptian Nile delta, a site which also probably supplied Roman glassmakers, is used to produce glass. The experiments show that high-quality glass, free of unreacted batch or bubbles, could have been produced from natron in its unprocessed form in a single stage, that larger quantities of natron would be required than has previously been anticipated, that the presence of different sodium-containing compounds in the deposit aided melting, and that negligible waste is produced. The implications for the identification of glass production sites, for the organisation of trade and for the supply of natron within and outside Egypt are discussed in the light of Pliny’s accounts.     

The palaeo-Christian glass mosaic of St. Prosdocimus (Padova,Italy): archaeometric characterisation of ‘gold’ tesserae

A systematic and extensive archaeometric study was carried out on the loose polychrome tesserae of the palaeo-Christian glass mosaic which decorated the votive chapel of St. Prosdocimus in Padova until its replacement by the current frescoes of Renaissance age and which is one of the only two known in the Veneto region (Italy). In particular, the present paper focuses on the ‘gold’ tesserae, i.e., tesserae with a metal foil, usually composed of gold, and characterised by transparent glass not deliberately coloured or decolourised. The main research aims were the identification of the ‘base composition’ of the glass used for mosaics and the reconstruction of production techniques. In addition, comparisons with major compositional groups identified in the literature allowed us to contextualise Paduan ‘gold’ tesserae in the wider context of glass production in the 6th century AD. The compositional characterisation of Paduan ‘gold’ tesserae, carried out by means of EMPA and LA-ICP-MS analyses, showed that most of the glass samples were obtained with natron as flux, although the coexistence of various production technologies and the extent of recycling, which confirm the 6th century AD as a period of technological transition, are documented. Identification of some soda ash tesserae also allowed us to attest Medieval restoration operations. The good match between compositional groups identified in the literature for glass vessels and compositional groups identified in the ‘gold’ tesserae suggests technological links between these two production types. The chemical similarity between ‘gold’ tesserae from Ravenna and some from Padova also links production technologies in these two towns during the 6th century; coupled with the results of the historical-artistic study, these factors provide further evidence to the hypothesis that the Paduan production was mainly influenced by the nearby city of Ravenna, the capital of Byzantine mosaics in Italy.     

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.     

Pliny the Elder and Sr–Nd isotopes: tracing the provenance of raw materials for Roman glass production

In Roman and Byzantine times, natron glass was traded throughout the known world in the form of chunks. Production centers of such raw glass, active from the 4th to 8th century AD, were identified in Egypt and Syro-Palestine. However, early Roman primary glass units remain unknown from excavation or scientific analysis. The ancient author Pliny described in 70 AD that besides Egyptian and Levantine resources, also raw materials from Italy and the Gallic and Spanish provinces were used in glass making. In this study, the primary provenance of 1st–3rd century AD natron vessel glass is investigated. The use of combined Sr and Nd isotopic analysis allows the distinguishing and characterizing of different sand raw materials used for primary glass production. The isotope data obtained from the glass samples are compared to the signatures of primary glass from known production centers in the eastern Mediterranean and a number of sand samples from the regions described by Pliny the Elder as possible sources of primary glass. Eastern Mediterranean primary glass has a Nile dominated Mediterranean Nd signature (higher than −6.0 ? Nd), while glass with a primary production location in the western Mediterranean or north-western Europe should have a different Nd signature (lower than −7.0 ? Nd). Most Roman glass has a homogeneous ⁸⁷Sr/⁸⁶Sr signature close to the modern sea water composition, likely caused by the (intentional) use of shell as glass raw material. In this way, strontium and neodymium isotopes now prove that Pliny's writings were correct: primary glass production was not exclusive to the Levant or Egypt in early Roman days, and factories of raw glass in the Western Roman Empire will have been at play.     

Innovation and tradition in the fourth century mosaic of the <Emphasis Type="Italic">Casa delle Bestie Ferite</Emphasis> in Aquileia,Italy: archaeometric characterisation of the glass tesserae

The present paper focuses on the archaeometric characterisation of 38 glass tesserae of various colours from an in situ mosaic in Aquileia, Italy, dated to the second half of the fourth century AD. The examination of the textural, mineralogical and chemical features, conducted by means of a multi-methodological approach (optical microscopy (OM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), electron probe micro analysis (EPMA), X-ray diffraction (XRD) and Fibre Optic Reflectance Spectrophotometer (FORS)), has provided valuable insights into the changes in the production technology during the transition between the Roman and the Late Antique periods. The assemblage is heterogeneous, and each chromatic group is composed of tesserae produced with different base glasses and colouring/opacifying techniques, suggesting diverse supplies. A small group of tesserae shows strict links to the Roman tradition in terms of both base glass and colouring/opacifying techniques and was probably obtained by re-using tesserae from older mosaics. Conversely, a larger group of tesserae shows textural and chemical evidence of recycling and indicates the prompt use of “new” opacifying technologies (such as the use of tin compounds) or uncommon technological solutions (such as the use of quartz and bubbles as opacifiers or the addition of metallurgical slags in red tesserae), suggesting a specific production in the fourth century AD.     

On Early Thimbles: A Seventh‐Century‐AD Example from Punta Secca,Sicily, in Context

A copper‐alloy thimble was found in 2010 at Punta Secca, Sicily, in a sealed context datable by coins to the first quarter of the seventh century AD. It has generally been thought that thimbles did not reach the Mediterranean area until the ninth century AD, but at least nine metal examples are in fact attested at various places from contexts datable between the late sixth century and the early ninth. It is suggested that the increasing use of silk in clothing in the Byzantine Empire during the seventh century, probably accompanied by the use for the first time of steel needles which made the use of a finger protector imperative, explains the apparent introduction of thimbles at this time. No securely dated metal thimbles are known from sites of Roman date, except for one at Ephesus of c.AD 100. It is very tentatively suggested that this last example might represent an import from China, where thimbles (and steel needles) are attested from at least the third century BC onwards.     

Byzantine glass mosaic tesserae: some material considerations

Abstract

Issues about the manufacture of Byzantine mosaics and the implications of these in wider terms relating to social and economic questions about the art form have been little discussed. This paper brings together evidence about Byzantine glass mosaic tesserae gathered from archaeology, glass technology and glass analysis, and synthesizes these into a discussion of three aspects: distribution; manufacture; trade and price. It looks to examine how these different elements can be used to form a more detailed composite picture about the production and distribution of Byzantine mosaics. It also proposes ways in which glass analysis can be used in a more coherent way to extend our understanding of mosaic glass production.     

ISOTOPES ON THE BEACH,PART 1: STRONTIUM ISOTOPE RATIOS AS A PROVENANCE INDICATOR FOR LIME RAW MATERIALS USED IN ROMAN GLASS‐MAKING

The provenancing of Roman natron glass is one of the most challenging problems in the field of archaeometry. Although the use of Sr and Nd isotope ratios and trace element signatures as an indication of provenance has proven promising, there are still many unknowns. In this study, the influence of the different raw materials on the final Sr isotopic composition of Roman natron glass is examined. It is shown that the ⁸⁷Sr/⁸⁶Sr ratio in natron glass is significantly influenced by the silicate fraction of the sand used and does not always provide a clear indication of the lime source used.     

Chemical composition characterization of ancient glass finds from <Emphasis Type="Italic">Troesmis</Emphasis>—Turcoaia,Romania

This paper reports and discusses the chemical composition of 20 glass fragments discovered during the 2012 archeological survey at Troesmis (Turcoaia, Tulcea county, Romania) and dated to the Roman and the Byzantine/Early Medieval periods. The data were obtained by two external Ion beam analysis (IBA) methods—namely Particle-induced X-ray emission (PIXE) and Particle-induced gamma-ray emission (PIGE)—and they were compared to the recognized compositional glass groups from the Mediterranean region during the first millennium AD. The Troesmis assemblage turned out to contain samples belonging to several distinct categories of ancient glass, obtained from different raw materials and manufacturing procedures. Some of the analyzed vitreous finds from Troesmis were the result of glass recycling, while others were identified as deriving from Roman glass vessels imported from the Levantine or Egyptian shores of the Mediterranean. This archeometric study brings additional arguments for the long-range commercial exchanges during the Roman period.     

BYZANTINE OPAQUE RED GLASS TESSERAE FROM BEIT SHEAN,ISRAEL*

This paper presents the results of analysis of Byzantine opaque red glass tesserae derived from three separate locations in the ancient city of Beit Shean, Israel. Investigation proceeded using reflective light microscopy, energy dispersive X‐ray fluorescence and energy dispersive scanning electron microscopy. The glass matrix of the tesserae was found to be heterogeneous, with many inclusions. Similarities and differences between tesserae from the two mosaics are examined and discussed. Implications for locale of manufacture and production techniques are considered. Comparisons between the three locations led to conclusions about the use of the tunnel as a storage site and the implications of this for future research on mosaics.     

Chemical characterisation and manufacturing technology of late Roman to early Byzantine glass from Beit Ras/Capitolias,Northern Jordan

The finding of considerable collections of glass artefacts, together with considerable lumps of glass chunks, fuel ash slag and kiln fragments related to glass processing strongly suggests a local secondary production (working) of glass at the Beit Ras/Capitolias archaeological site in northern Jordan from the late Roman to the early Byzantine period. The chemical analysis of ancient glasses can provide important information regarding the manufacturing technology of the glass made during a specific period. The aim of this study is to characterise the chemical and technological aspects of late Roman to early Byzantine glasses excavated from this main archaeological site. Furthermore, the present paper aims to provide incontrovertible evidence that this site must be considered as a major centre for the secondary production of glass during a period between the 3rd and the 6th centuries. For this purpose, a considerable group of raw glass chunks and vessel fragments of different colours and typologies were collected. The results of chemical analyses indicated that the glass did not show a clear difference in chemical composition between late Roman and early Byzantine times. All the glasses (artefacts and chunks) are of the soda-lime-silica type and correspond to the previously defined Levantine I glass group. The chemical composition of the glass chunks, identical to that of contemporary glass of the same colour, strongly suggests that these chunks were used for the manufacture of late Roman to early Byzantine glass at Beit Ras. The observation of technological features indicates that glass chunks were produced in massive tank furnaces in other primary production centres elsewhere, and were meant for local reworking. According to the microscopic examination, it can also be observed that mould-blowing was the main technique used for forming glass.     

The Production and Circulation of Carthaginian Glass Under the Rule of the Romans and the Vandals (Fourth to Sixth Century ad): A Chemical Investigation

Fifty‐seven glass samples from Carthage dating to the fourth to sixth century ad were analysed using the electron microprobe. The results show that these samples are all soda–lime–silica glass. Their MgO and K₂O values, which are below 1.5%, suggest that they were made from natron, a flux that was widely used during the Roman period. The major and minor elements show that these samples can be divided into four groups, three of which correspond to the late Roman period glass groups that were found throughout the Roman Empire: Levantine I, and ‘weak’ and ‘strong’ HIMT. Of particular interest is our Group 2, which is technologically and compositionally similar to HIMT glass and the CaO and Al₂O₃ values of which are similar to those of Levantine I. Glass of similar composition has been reported by several authors and is predominantly found dating from the late fifth to seventh century. This could represent a ‘new’ glass group; therefore further study is needed to determine its origin. Also, this study suggests that the Vandal invasion in North Africa did not disrupt the glass trade between Carthage and the Levantine coast.     

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.     

The palaeo-Christian glass mosaic of St. Prosdocimus (Padova,Italy): archaeometric characterisation of tesserae with antimony- or phosphorus-based opacifiers

The present paper reports the results of archaeometric characterisation of the opaque tesserae, intentionally coloured with antimony- or phosphorus-based opacifiers, coming from one of the two only palaeo-Christian glass mosaics known in the Veneto region (Italy), i.e., the mosaic which decorated the votive chapel of St. Prosdocimus in Padova. In particular, 55 tesserae belonging to glass types “White”, “Blue”, “Yellow”, “Green” and “Brown” are examined here. The multi-methodological approach (SEM-EDS, EMPA, XRPD, imaging spectroscopy coupled, in some cases, with XAS) gave valuable insights into the complexities of palaeo-Christian glass mosaic production technologies. Two main groups are identified, one characterised by glassy matrixes and opacifiers (calcium or lead antimonate) typical of the Roman period and comprising all “White”, “Blue”, and “Yellow” tesserae and some “Green” ones, and the other characterised by glassy matrixes and an opacifier (calcium phosphate) typical of the 6th century AD, composed of “Green” and “Brown” tesserae. This suggests that, during that century there was a gradual change from older to “new” production technologies: although new opacifiers such as calcium phosphate started to be used, the frequent use of antimony-based ones (43/55 samples) supports the hypothesis that their systematic use was extended until the 6th century, although re-using old tesserae cannot be completely excluded. In addition, comparisons with compositional groups already identified in the “gold” tesserae of the same mosaic and tesserae from Ravenna demonstrate that both the same “base compositions” of the glass were used to produce transparent and opaque glass. This evidence, coupled with the results of the historical-artistic study, suggests technological connections between Padova and Ravenna, the capital of Byzantine mosaics in Italy. Micro-structural observations and chemical analyses of the Paduan antimony-based opacified glass demonstrate that different processes and raw materials were used in their production. Both in situ and ex situ crystallisation can be identified for calcium and lead antimonate in Paduan tesserae, whereas the production of tesserae opacified with calcium phosphate generally appears to be highly standardised. Although the opacifiers used in the Paduan tesserae support technological transitions, the colouring elements identified here, i.e., iron and manganese for white, yellow, brown and some green tesserae, cobalt for blue, and copper for blue and green, suggest continuity, because their use is widely testified in the production of both transparent and opaque glass artefacts dating from the Bronze Age until Medieval times, from whichever archaeological site the samples come. Peculiar relationships among the oxidation states of colouring elements, their contents in the glassy matrix, the types of opacifiers used, and the final colour of tesserae were identified. In addition, the correlations of cobalt and/or copper with other elements, together with identification of relics of colouring and “metallic” droplets, allow us to speculate on possible sources and production technologies. Lastly, identification of newly formed crystalline inclusions in tesserae also yields information on kiln temperatures, which ranged between 900 and 1150 °C, a range easily reached in the furnaces of the 6th century AD.     

δ18O measurements of archaeological glass (Roman to Modern age) and raw materials: possible interpretation

The present paper reports results from a systematic study of oxygen isotopic compositions for glass samples from various archaeological sites (i.e., Iulia Felix, Grado, Vicenza, Pozzuoli and Modena in Italy, and Derrière Sairoche in Switzerland) and dated from the Roman period to the 18th century AD, as well as of some raw materials that may have been used for their production. The analysed samples differ essentially in the type of flux, using Roman and high Medieval glass natron and late Medieval and modern glass plant ash, soda and potash, respectively. The aim of this study was to amplify the database of oxygen isotope data for various archaeological glasses and to identify isotopic trends indicating different raw materials, production technology, and/or provenance. Results indicate that natron glass samples of various provenance and age have consistently higher δ¹⁸O values than plant ash ones (about 15.5‰ vs 13.0‰), probably due to the different flux, highly ¹⁸O-enriched in the case of natron. Isotopic data on Belus and Campanian sands, the types mentioned by Pliny for glass production, show that they have similar isotopic composition. Taking into account the oxygen isotopic composition of Roman glass, the “positive natron effect”, and the negligible influence of small amounts of manganese and antimony containing decolourisers, the suitability of both sources for glass production is verified, supporting the hypothesis of multiple sand sources. Notwithstanding this, the isotopic similarity between Belus and Campanian sands prevents us from identifying the starting material from the δ¹⁸O of the final product. In the case of plant ash used as flux, it is not possible to distinguish between soda and potash plant ash, because the addition of ash did not contribute isotopically heavy oxygen and the silica source is presumed to be comparable in the analysed samples. The isotopic data of the present study are also compared with those already published in the literature, and possible interpretations on their analogies and differences are discussed.     

Supply routes and the consumption of glass in first millennium CE Butrint (Albania)

Archaeological, historical and analytical evidence can identify trade patterns and the movement of people and products and thus reveal the cultural and economic connections that existed at a given time. In the case of first millennium CE glass, the manufacture of raw glass in a limited number of glass making installations with unique compositional characteristics makes it possible to trace the likely origin of the raw materials at consumption sites. In this way the analytical characterisation of a large corpus of glass finds can identify changes in the supply routes of high-end industrial products from the Roman to the middle Byzantine period.     

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.