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.     

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

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

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.     

The glass of Nogara (Verona): a “window” on production technology of mid-Medieval times in Northern Italy

The site of Nogara (province of Verona, Italy) provides valuable insights into the complexities of the glass industry in mid-Medieval times, due to its timing, which ranges mainly between the 10th and 11th centuries AD, and to the great quantity of glass findings, mainly tableware. In the present paper, the combination of archaeological, chemical and textural data allows us to identify production technologies in a time-interval perceived to be a period of technological transition for glass. In particular, the frequent occurrence of recycled natron glass and only a few glass samples made with soda plant ash indicate that recycling of earlier glass was common in inland Northern Italy in the 10th–11th centuries AD. In addition, blue and reticello decorations were obtained by recycling earlier glass mosaic tesserae, as shown by much Co, Cu, Sn, Sb and Pb and the presence of crystallised calcium antimonates. A few glass samples with chemical compositions intermediate between natron and soda plant ash glass were also identified, suggesting a gradual change in glass composition from natron-based towards soda ash-based production technology, which prevailed in the 13th-14th centuries. In conclusion, the difficulty in describing mid-Medieval glass as a well-defined entity, due to the great propensity for recycling earlier glass samples which causes variability in chemical compositions, particularly those of trace elements, is clearly documented here. In any case, this paper contributes to a new type of chrono-typological scanning and to more detailed knowledge of glass production technology during mid-Medieval times in Northern Italy, little found in the literature until now.     

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.     

Electron Microprobe Analysis of 9th–12th Century Islamic Glass from Córdoba,Spain

Twenty‐six samples from domestic assemblages of 9th–12th century Córdoba were subjected to electron microprobe analysis. The results reveal two main compositional types. The first, encountered in 13 of the samples, seems to result from the combination of plant ashes with high‐impurity sand, and has some contemporary parallels from Syria and Egypt. The second type is a lead–soda–silica glass, encountered in a relatively high proportion of the glasses (11 of the 26 sampled), possibly formed by the addition of lead metal to existing glasses and with very few known parallels. These are among a very small number of results available to date on the chemical composition of glasses from medieval Spain, and the presence of a high proportion of lead–soda–silica glasses is particularly interesting, possibly indicating a technological practice unique to, or originating in, the western Muslim world.     

Egyptian faience glazing by the cementation method part 2: cattle dung ash as a possible source of alkali flux

Based on our current awareness, there are three distinct primary sources of alkali flux in the ancient Egyptian faience making: natron, soda rich plant ash and the so-called ‘mixed alkali fluxes’. Whereas the nature and origin of the first two types are identified to some extent, there are more questions regarding mixed alkali fluxes. In an attempt to provide further clarification on the latter source, a series of replication experiments on the production of Egyptian faience by the cementation glazing method were conducted using cattle dung ash as the source of alkali flux. After firing at 980 °C, the appearance of the faience objects, the microstructure and the chemical composition of selected samples obtained using scanning electron microscopy/energy-dispersive spectroscopy (SEM-EDS) were investigated. The discussion has primarily focused on cattle dung ash as the most, or one of the most, available sources of ash in ancient societies and its possible use as a source of alkali flux in the production of Egyptian faience, at least by the cementation glazing method.     

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.     

Different glassmaking technologies in the production of Iron Age black glass from Italy and Slovakia

This study presents the results of an archaeometrical investigation performed on 75 black glass beads dated to the ninth–fifth century BC coming from Bologna, Cumae, and Pozzuoli (Italy), and Chotin (Slovakia). The analyses of the major, minor, and trace elements—as well as that of Sr and Nd isotopes performed on a selection of samples coming from Bologna—provided evidence for two different production technologies in Iron Age black glass found in Italy (natron glass, probably produced in Egypt) and Slovakia (wood ash glass, probably produced in Europe). In both cases, the glasses derive their black colouration from the high presence of iron (around 12 % FeO), introduced into the glass batches through the intentional choice of dark sands. The production model appears to be small-scale and experimental, characterised by the use of non-sorted raw materials and poorly defined formulae, producing glass with a high chemical variability. The wood ash technology appears to have dropped out of use in Europe until the Medieval period, while natron production spread quickly, becoming predominant throughout the Mediterranean.     

Natron as a flux in the early vitreous materials industry: sources,beginnings and reasons for decline

Natron deposits, the best known of which being those at Wadi Natrun in Egypt, have been used as the flux in the production of vitreous materials from the early 4th millennium BC onwards. In the present paper, the history of the use of natron as a flux is traced from its beginnings in the glaze of Badarian steatite beads, through its use in glass production starting in the 1st millennium BC, until its apparent shortage during the 7th to 9th centuries AD, and its subsequent replacement by plant ash during the 9th century AD. Documentary evidence for possible natron sources in Egypt, including the Wadi Natrun, and around the eastern Mediterranean is summarised, and the results of recent fieldwork at the Wadi Natrun and at al-Barnuj in the Western Nile Delta are presented. The possible reasons for the apparent shortage of natron from 7th to 9th centuries AD and its subsequent replacement by plant ash as the flux used in glass production during the 9th century AD are then considered. These include the possibility that, because of the massive scale of glass production, the demand for natron exceeded its supply; the possible effect of climatic changes; and the potentially disruptive role of political events in the Wadi Natrun–Delta region.     

A COMBINED MULTI‐ANALYTICAL APPROACH FOR THE STUDY OF ROMAN GLASS FROM SOUTH‐WEST IBERIA: SYNCHROTRON μ‐XRF,EXTERNAL‐PIXE/PIGE AND BSEM–EDS

An integrated, multi‐analytical approach combining the high sensitivity of SR‐μXRF, the light element capability of PIXE/PIGE under a helium flux and the spatial resolution of BSEM + EDS was used to characterize chemical composition and corrosion of glass samples (first to fourth centuries ad ) from an important, but scarcely investigated, Roman region of south‐west Iberia (southern Portugal). The geochemical trends and associations of major, minor and trace elements were investigated to shed light on production techniques, the provenance of raw materials and decay mechanisms. The results, while confirming a production technique common to Roman glasses throughout the Empire—that is, a silica‐soda‐lime low‐Mg, low‐K composition, with glass additives as colouring and/or decolouring agents (Fe, Cu, Mn, Sb)—show at one site high Zr–Ti contents, suggesting a more precise dating for these glasses to the second half of the fourth century. The Ti–Fe–Zr–Nb geochemical correlations in the pristine glass indicate the presence of minerals such as ilmenite, zircon, Ti‐rich Fe oxides and columbite in the sands used as raw materials for the glass former: these minerals are typical of granitic‐type source rocks. The unusually high K content in the corrosion layers is consistent with burial conditions in K‐rich soils derived from the alteration of 2:1 clays in K‐bearing rock sequences.     

CHARACTERIZATION AND PROVENANCE OF LATE ANTIQUE WINDOW GLASS FROM THE PETRA CHURCH IN JORDAN*

Fifth‐ to seventh‐century window glass fragments from the Petra Church in Jordan were analysed by EPMA and spectrophotometry to characterize their optical properties and chemical composition. The objective of this study was to determine the provenance of the raw glass and the secondary production procedures of the window‐panes. Judging from the material evidence, both the crown window‐panes and possibly the rectangular samples were produced through glass‐blowing techniques. The chemical data show that the assemblage forms a homogeneous group of soda–lime–silica glass of the Levantine I type. The green glass, however, has higher silica and lower soda contents than the aqua‐blue fragments. The composition of one sample suggested the recycling of Roman glass. Our results confirm the trade of glass between the Levantine coast and Petra during Late Antiquity. No colouring agents other than iron were detected. Spectrophotometry confirmed the presence of iron and showed that the window fragments absorbed light relatively equally across the visible part of the spectrum. The windows thus seem to have provided an almost colourless illumination for the sacred interior.     

The colourless glass of Iulia Felix

The present paper focuses on 85 colourless glass samples selected among the recycling cullet found 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, with the aim of examining their chemical composition, investigating similarities within and between the three established group types (cups, plates, bottles), and comparing the chemical compositions of the Iulia Felix glass samples with groups reported in the literature for colourless glasses. Chemical analyses, performed by X-ray fluorescence and electron microprobe, indicate that the samples were all soda-lime–silica in composition, with natron as flux, according to typical Roman production technologies. Chemical data are treated by multivariate statistical tools, such as cluster analysis and the NPC test. Statistical analyses allow us to conclude that the Iulia Felix colourless glasses were produced by at least two different production technologies related to group type, confirming the trend recently identified in the literature. In addition, the trace element patterns (particularly those of Sr, Zr and Ba) suggest that beach sand with differing amounts of alkali feldspars was predominantly used as raw material, like those specifically mentioned by Pliny for glass production.     

An archaeometric study of the bulk and surface weathering characteristics of Early Medieval (5th–7th century) glass from the Po valley,northern Italy

Compositional and structural characterisation was carried out on Early Medieval (5th–7th century) fragments of glass goblets excavated from the archaeological sites of Monte Barro, Brescia and Monselice (northern Italy) with the aim of identifying raw materials, glass-working techniques, and surface weathering characteristics. Optical analyses and X-ray spectrometry were used for bulk, and X-ray photoelectron spectroscopy and scanning and transmission electron microscopy for surfaces. The samples of each area were produced using siliceous–lime sands, with natron as flux. The differences observed in chemical composition allow to subdivide the samples from Monte Barro and Brescia from those of Monselice, the latter generally show higher silicon, calcium and aluminium and lower sodium contents than the others. By plotting reduced base glass compositions in soda–lime silica phase diagrams, melting temperatures varying from 900 °C for Monte Barro and Brescia samples to 1000 °C and more for those from Monselice were estimated. Differing Fe₂O₃, Sb₂O₅and MnO₂contents are related to the different colours of the samples, Monselice samples being blue–green and Monte Barro and Brescia samples green and yellow–green. The chemical differences may be interpreted as related to different provenance and/or glass-working techniques. Surfaces are depleted in alkaline and alkaline-earth elements due to weathering process. Alteration lamellae show a nanostructure, similar to that of opal.     

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.     

AN ASSESSMENT OF COMPOSITIONAL AND MORPHOLOGICAL CHANGES IN MODEL ARCHAEOLOGICAL GLASSES IN AN ACID BURIAL MATRIX

The degradation mechanisms of glass in a buried context result in surfaces that have been depleted in various elements. The stability of the glass is primarily affected by the burial environment and the glass composition. However, in all archaeological glasses, the corroded layer that is formed on the surface tends to be low in alkalis, high in silica and lacking in cohesion. The extent to which the material has degraded, along with the physical nature of the corrosion, has a profound effect upon a wide range of factors affecting the stability of artefacts, as well as the choice of conservation techniques to be employed. This study has a number of objectives: determination of the morphology of the surface of the leached layer in glasses of two different compositions with different surface finishes; examination of the transition between the corroded material and the unaffected substrate; and investigation of concentration profile of different elements within the surface layers, as a function of depth. The study uses two glasses, fabricated under laboratory conditions, to replicate two common glass types found in the historical environment; a soda–lime–silica glass typical of those found in the Roman period throughout the Mediterranean and northwestern Europe, and high‐lime–potash glasses typical of those of Western Europe in the late medieval period. Three different surfaces have been prepared to mimic alternative manufacturing techniques such as blown, cast and ground surfaces for each composition. The glasses have been corroded under controlled laboratory conditions to replicate the buried environment. Imaging and chemical information is obtained using SEM–EDX and morphological information using IFM to produce 3‐D mapping from topographical surfaces.     

Analysis of Medieval and Post‐Medieval Glass Fragments from the Dubrovnik Region (Croatia)

Dubrovnik was an important trade city throughout the medieval and post‐medieval time period, maintaining its own glass production from the 14th to the 16th century. Unfortunately, Dubrovnik glass discoveries have not been well investigated up until now, except via archival data in large data analyses. In the following work, we will shed new light on the glass material found in this region, which has diverse origins, chronology, typology and style. Medieval and post‐medieval glass finds (10th/12th–18th centuries) discovered during archaeological excavations in Dubrovnik and the Dubrovnik region were analysed using particle‐induced X‐ray emission (PIXE) and particle‐induced gamma‐ray emission (PIGE), which revealed three main compositional groups: natron glass, plant‐ash glass and potash glass. This demonstrates the important commercial links present between Dubrovnik and other major glass‐making centres.     

Change in chemical composition of early Islamic glass excavated in Raya,Sinai Peninsula,Egypt: on-site analyses using a portable X-ray fluorescence spectrometer

The Raya port (eighth to 12th centuries) on the Sinai Peninsula, Egypt, was one of the important port cities for the Red Sea trade. We performed on-site analyses of Islamic glass vessels (used in eighth to 11th centuries) mainly from this site in Egypt using a portable XRF spectrometer. The aim of this paper is to contribute to our understanding of the chemical compositions of early Islamic glass vessels by comparing their archaeological date and typology. In the early Islamic period, glass objects were mainly produced from natron as the soda source. Among the natron glass analyzed in this study, glass vessels with low titanium and iron and high strontium contents, which were probably produced in the Syria–Palestine region, were excavated in the eighth century layer. From the ninth century layer, a large number of samples with high levels of calcium, titanium and iron, probably produced in Egypt, were found. It should be noted that a large number of glass vessels with this chemical composition were found at the Raya site, because this type of glass was rarely reported from other Islamic sites. We finally concluded that this type of glass seems to be produced under a fixed recipe, although some samples contain a colorant or decolorized materials.     

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.     

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.