Evidence for glass ‘recycling’ using Pb and Sr isotopic ratios and Sr-mixing lines: the case of early Byzantine Sagalassos

The secondary production (working) of glass from imperial to early Byzantine times has been proven at the ancient city of Sagalassos (SW Turkey) by the existence of glass chunks, fuel ash slag and kiln fragments related to glass processing. It had been previously suggested that local green glass might have been recycled from two other locally found glass types (blue glass vessels and chunks and HIMT glass chunks). This paper provides analytical evidence for the recycling of glass next to the use of imported raw glass. The heterogeneous lead isotopic composition of the green and HIMT vessel glass at Sagalassos, with as end members on the one hand the isotopic composition of local blue glass vessels and chunks and on the other hand that of the HIMT glass chunks, could indicate the production of ‘recycled’ glass, although heterogeneous raw materials could have been used. However, the use of Sr-mixing lines confirms local recycling. It is clear that the Sr in the green and HIMT vessels is a mixture of the Sr in the aforementioned end members. It cannot be proved whether the green ‘recycled’ glass was produced from a mixture of chunks alone, or from a mixture of cullet and chunks. Suggestions are made towards the possible origin of the raw materials for the blue and HIMT glass on the basis of Sr isotopic signatures and absolute Sr contents in the glass.     

TRACING THE RESOURCES OF IRON WORKING AT ANCIENT SAGALASSOS (SOUTH‐WEST TURKEY): A COMBINED LEAD AND STRONTIUM ISOTOPE STUDY ON IRON ARTEFACTS AND ORES*

Lead and strontium isotope analyses were performed by thermal ionization mass spectrometry (TIMS) on Roman to Byzantine iron artefacts and iron ores from the territory of ancient Sagalassos (south‐west Turkey), to evaluate Pb and Sr isotopes for provenance determination of ores for local iron production. It can be demonstrated that for early Roman artefacts and hematite iron ore processed in early Roman times from Sagalassos proper, as well as for magnetite placer sands and early Byzantine raw iron from the territory of the city, Sr isotopes are much less ambiguous than Pb isotopes in providing clearly coherent signatures for ore and related iron objects. Late Roman iron objects were produced from iron ores that as yet remain unidentified. Early Byzantine iron artefacts display more scatter in both their Pb and Sr isotope signatures, indicating that many different ore sources may have been used. Our study demonstrates that iron objects can be precisely analysed for their Sr isotopic composition, which, compared to Pb isotopes, appears to be a much more powerful tool for distinguishing between chronological groups and determining the provenance of raw materials.     

Combined Pb–Sr isotopic analysis in provenancing late Roman iron raw materials in the territory of Sagalassos (SW Turkey)

In early Roman times, iron was likely supplied to the city of Sagalassos through the smelting of close-by hematite ores. In the early Byzantine period, magnetite–titanite placer sands in some instances could have been exploited for its iron. For the intermediate late Roman period, however, the source of the locally used iron was unknown. Pb and Sr isotopic analyses of iron ores from the area of Camoluk, just south of the territory of Sagalassos, and of late Roman iron artefacts from the antique city itself, reveal a very close resemblance. This makes the use of the Camoluk ores to supply Sagalassos with raw iron in the late Roman period likely. It is also shown that combined Pb and Sr isotopic analyses provides a powerful tool to distinguish chronological groups of iron provenance and a technique that can determine the nature and source of iron raw materials used.     

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.     

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.     

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.     

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.     

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.     

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.     

ARCHAEOMETRICAL INVESTIGATION OF SICILIAN EARLY BYZANTINE GLASS: CHEMICAL AND SPECTROSCOPIC DATA*

A series of early Byzantine glasses, recovered in Ganzirri (Sicily, Italy), was analysed for major, minor and trace elements. All the analysed fragments were found to be natron-based silica–lime glass. Concerning minor and trace elements, the samples can be divided into two groups: glass with high Fe, Ti and Mn contents ( HIMT glass) and glass with low levels of Fe, Ti and Mn. These results, strictly in agreement with literature data for glass of the Mediterranean region, can be interpreted as a consequence of the wide trade network established in this region and of the intense circulation of raw glass and artefacts from different Mediterranean areas. X-ray absorption spectroscopy studies at Fe and Mn K-edges, performed on HIMT glass, indicate that Fe is in the oxidized form while Mn is in the reduced form.     

The origins of Byzantine glass from Maroni Petrera,Cyprus

Nineteen glasses from Maroni Petrera, Cyprus, dating to the sixth–seventh centuries ad, have been analysed by energy‐dispersive X‐ray analysis in the scanning electron microscope for major and minor elements. A subset of 15 glasses was also analysed for trace elements, using inductively coupled plasma mass spectrometry. Two groups are identified. The majority is made of glass produced in the coastal region of Syria–Palestine. The smaller group is of high iron, manganese and titanium (HIMT) glass, a widespread type of uncertain origin at the present time. The glasses appear to have undergone relatively minor mixing and recycling, and the glass material is likely to have arrived in Cyprus in the form of raw glass chunks or relatively fresh vessel cullet.     

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.     

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.     

Investigations of Byzantine glass bracelets from Nufăru,Romania using external PIXE–PIGE methods

The chemical composition of twenty glass bracelet fragments found in Nuf?ru, a Byzantine site from 10th–13th centuries A.D., nowadays located on Romania's territory, has been determined using Particle Induced X-ray Emission (PIXE) and Particle Induced Gamma-ray Emission (PIGE) in external beam mode. Most of the Byzantine bracelet fragments were identified as “mixed natron-plant ash” soda-lime-silica glasses. The obtained chemical compositions indicated that the manufacturing of these finery items was performed using similar raw materials and techniques, in most of the cases involving colored glass recycling. PIXE–PIGE results highlighted the glass chromophores (cobalt, manganese, copper and iron ions) and provided hints about the mineral pigments used to paint the external surface of some bracelets.     

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.     

The Reliquary Bust of Saint Lambert from the Liège Cathedral,Belgium: Gemstones and Glass Beads Analysis by pXRF and Raman Spectroscopy

The reliquary bust of Saint Lambert, hosted in the Treasure of the Liège Cathedral, was produced in the early 15^th century. This exceptional goldsmithery piece is covered with gold-coated silver, and decorated by approximately 400 stones, analysed by Raman and pXRF techniques to determine their mineralogical and chemical composition. The results confirm the identification of one hundred pearls, twenty-six rock crystals, ten amethysts, two diamonds, and numerous glass beads with a green, blue, colourless, turquoise, orange or red colour. The glass beads show a soda-lime composition, confirming that they are contemporary of the bust and imported from Venice, as reported by historical sources. Orange beads show a lead composition and the red stone a triplet with quartz, indicating that they were added to the bust later. The cutting of gems and beads shows also a significant evolution. The metal contains approximately 60% of Au and 40% of Ag. The origin of gemstones was difficult to establish, due to the absence of characteristic trace elements, but the chemical elements used for the manufacture and colouring of the beads were determined. This study confirms the trade of stones between Liège and Venice during medieval times.     

MAKING COLOURLESS GLASS IN THE ROMAN PERIOD*

This paper discusses the compositional analysis of Roman colourless glass from three sites in Britain. The findings suggest that two broad compositional groups can be identified on the basis of the choice of the initial raw materials selected for glass production, in particular the sand. The largest of these groups is inherently different from the naturally coloured, blue–green glasses of the same period, while the other group is compositionally similar. Further subgroups are apparent on the basis of the decolorizers used. These glass groups are explored in the light of the current theories concerning the organization of glass production in the Roman world.     

New insights into Byzantine glass technology from loose mosaic tesserae from Hierapolis (Turkey): PIXE/PIGE and EPMA analyses

This study focuses on the Byzantine glass tesserae from Hierapolis (Phrygia, central Turkey). Fifty-seven samples of loose tesserae from two sites in the town (the theatre and the church of St. Philip) are analysed by particule-induced X-ray emission and particule-induced gamma ray emission and electron probe X-ray microanalysis to obtain the chemical composition and identify the colourants and opacifiers. The aims are to add new information to the scant knowledge of the Byzantine glassmaking technology, to constrain the chronology of the mosaics and to trace the supply routes of the tesserae. In the destruction layers of the theatre, tesserae produced following the Roman glassmaking technology (natron glass opacified by calcium and lead antimonate) were found. They were made using a Levantine 1 raw glass, generally attributed to the early Byzantine period (fifth to sixth c.). In the church, the samples attest a technological change from Roman tradition, and a complex pattern according to building history (two phases are attested, probably in the sixth and eighth to ninth c.), and a multiplicity of supply. Three glass types and some recipes not attested before in this chronological range for the production of tesserae are documented, such as the use of a local low-chlorine natron glass for the production of black and red tesserae, the blue colouring by a source of cobalt with zinc in a natron glass tessera and the opacification with tin oxide (both in a lead-free and in a high-lead natron glass), as well as with quartz.     

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.     

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.