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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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 APPLICATION OF A PORTABLE X‐RAY FLUORESCENCE SPECTROMETER TO THE ON‐SITE ANALYSIS OF GLASS VESSEL FRAGMENTS FROM SOUTHERN THAILAND*

Ancient glass vessel fragments belonging to the seventh to ninth centuries ad , from the Ko Kho Khao, Laem Pho and Khuan Lukpad sites in southern Thailand, were studied. The glass vessel fragment samples are a collection belonging to the Department of Archaeology, the 15th Regional Office of Fine Arts of Thailand. The chemical compositions of the glasses were analysed using a modified portable energy‐dispersive X‐ray fluorescence spectrometer (OURSTEX 100FA‐II) by the introduction of a MOXTEK^® AP3.3 polymer window (5 mm²?) to the KETEK silicon drift detector for the measurement of light elements. The non‐destructive analysis was performed at the National Museum, Phuket, in Thailand. It is shown that the glass chemical compositions belong to mineral and plant‐ash based soda–lime–silicate glass. The origins of the glass artefacts are discussed in terms of raw materials and glass decoration, and compared with previously reported similar typological glasses from sites in the port city of Rāya and the Monastery of Wadi al‐Tur in Egypt.     

Production Technology for Copper‐ and Cobalt‐Blue Vitreous Materials from the New Kingdom Site of Amarna—A Reappraisal*

Previously published data on the chemical compositions and microstructures of copper‐ and cobalt‐blue frit, glass and faience from the New Kingdom site of Amarna in Egypt ( Shortland 2000 ) are summarized. The data are then used to infer the raw materials and processes employed in the production of these vitreous materials. The results suggest that crushed quartz pebbles were the source of the quartz for all the materials, but that different sources of alkali, both natron and a range of plant ashes, were used in the production of each material. It seems probable that the cobalt‐rich alum colorant was pre‐treated before use by precipitating cobalt hydroxide from a solution of the alum by the addition of natron. It is further hypothesized that cobalt‐blue glass was produced by melting the cobalt‐blue frit together with additional plant ash and possibly quartz. Finally, it is suggested that, in glazing the cobalt‐blue Variant D faience first produced in the 18th Dynasty, the efflorescence or application method was selected according to object type.     

The Chronology of Insiza Cluster Khami‐Phase Sites in South‐Western Zimbabwe: Compositional Insights from pXRF and Raman Analysis of Excavated Exotic Glass Finds

Fourteen glass beads and one glass fragment from Khami‐period (ad 1400–1830) sites of Danamombe, Naletale, Gomoremhiko, Nharire and Zinjanja, in Zimbabwe, were analysed by pXRF and Raman spectroscopy with the intention of correlating the results with associated radiocarbon dates. The results show that Zinjanja and an earlier part of the Danamombe stratigraphic context had Khami Indo‐Pacific beads (15th–17th centuries) corresponding with Torwa occupational layers. Other European beads and one bottle fragment [high‐lime, low‐alkali (HLLA) glass] dating from the 16th to the 19th centuries were confined to the top stratigraphic layers of Danamombe and Naletale, which coincide with the later Rozvi occupational layers. Gomoremhiko had one Mapungubwe–Zimbabwe bead series (13th–15th centuries), which suggests that it was probably earlier than the other sites. All European beads are made of soda–lime plant‐ash glass with high alumina, which makes them comparable with glass produced through the Mediterranean traditions in Southern Europe.     

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.     

The composition of ‘naturally coloured’ late Roman vessel glass from Britain and the implications for models of glass production and supply

Naturally coloured, blue or green are the most common glass colours found in assemblages from the Roman world from the end of the 1st century BC onwards. In the 4th century two different compositions have come to dominate this group, ‘HIMT’ and ‘Levantine 1’ glasses, both of which are now thought to have been produced in the eastern Mediterranean. Using Romano-British glass assemblages from the 4th and 5th centuries, it is shown here that although the two naturally coloured glass types predominate, by far the most common composition in British assemblages is HIMT, although older, earlier blue-green compositions are still present. The earliest date HIMT could be identified in these assemblages is around AD 330, although two distinct compositions can be identified within this group which relate to changes in composition over time. A similar change over time is seen in the Levantine 1 glasses. The reasons for these patterns within the assemblages are explored within the archaeological evidence currently available for glass production and consumption in the Roman world.     

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.     

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

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

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.     

The Mediterranean Group II: analyses of vessels from Etruscan contexts in northern Italy

A large number of Mediterranean Group vessels were recovered at the Etruscan site of Spina in northern Italy and dated from the 6th to the 3rd century BC. In this work a number of vessels belonging to the so-called “Group II” were analysed. The samples are mainly Alabastra, Oinochoai, Amphoriskoi, and Hydriai, in general opaque and deeply coloured. The aims of this study are: 1) to characterize these samples since there is a lack of data in literature regarding Mediterranean Group II; and 2) to compare the data obtained with that of glass for previous centuries (Mediterranean Group I) recovered at the same site in order to establish whether they could have the same origin. The chemical analyses of major and minor elements were carried out by electron microprobe and the nature of the opacifying and colouring agents was determined by X-ray diffraction. The sample set is relatively homogeneous and most of the samples can be classified as Low Magnesium Glass produced with natron and a calcareous silicatic sand. The XRD analyses proved the use of lead antimonates in the manufacture of yellow decorations and of calcium antimonates in the white and light blue decorations. The consistency of the chemical compositions of Mediterranean Groups I and II samples makes it possible to hypothesize a common origin.