THE COLOURED TESSERAE DECORATING THE VAULTS OF THE FARAGOLA BALNEUM (ASCOLI SATRIANO,FOGGIA, SOUTHERN ITALY)

Twenty‐six tesserae (red, orange, yellow, light amber, green, blue and white) from the balneum of the villa at Faragola (Ascoli Satriano, Foggia) have been examined by colorimetry, ICP–MS, ICP–OES and SEM–EDS. Different types of calcareous sands have been used as the source of silica (network former), also providing the stabilizing agent. A natron‐type soda source served as the network modifier; however, the use of a sodium‐rich plant ash and the recycling process have been hypothesized for the production of two tesserae (FT 1 red and FT 3 orange). The colouring and opacifying agents were Cu oxide (cuprite, orange), metallic copper (red), Pb antimonates (yellow), Ca antimonates (white), a mixture of copper (Cu²⁺) and Pb antimonates (green), a mixture of cobalt (Co²⁺) or copper (Cu²⁺) and Ca antimonates (blue). The light amber tesserae should owe their colour to iron (Fe³⁺) alone or associated with sulphide (S^2?) and Ca antimonates. It is likely that the Faragola tesserae were locally produced in a secondary glass workshop.     

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.     

MOSAIC GLASS FROM ST PETER'S,ROME: MANUFACTURING TECHNIQUES AND RAW MATERIALS EMPLOYED IN LATE 16TH‐CENTURY ITALIAN OPAQUE GLASS

A recent restoration of late 16th‐century mosaics in one of the vaults beneath the dome of St Peter's Basilica in Rome allowed sampling and analysis of a group of glass tesserae. The aim of this work is the characterization of opaque coloured glasses possibly produced in Rome. The characteristics of the glass from St Peter's were compared with those of Venetian and Tuscan production, in order to assess possible common origins. Chemical analysis of 30 samples was carried out by electron microprobe, while the nature and morphology of opacifiers were determined by X‐ray diffraction and scanning electron microscopy. Almost all the opaque samples were characterized by the presence of SnO₂ crystals. In addition, depending on the colour of the glass, other crystalline phases were identified: lead‐tin oxide (PbSnO₃) in yellow glass, cuprite (Cu₂O) in orange glass and two calcium‐tin silicates with different stoichiometry (CaSnSiO₅ and Ca₃SnSi₂O₉) in the green‐yellow variety. A frame of reference for identifying raw materials and glass‐making techniques is provided by textual sources, here examined in comparison with the compositional characteristics of the tesserae from St Peter's.     

Rationales in Old World Base Glass Compositions

It is long known that most Egyptian and Roman base glass compositions show a remarkably small scatter in their chemical composition. By plotting appropriately reduced base glass compositions in ternary phase diagrams it is demonstrated that the compositional fields defined by the compositional scatter are closely related to eutectic regions within the relevant phase diagrams. This is interpreted as to be due to an eutectic melting regime, i.e. partial melting in the presence of a crystalline buffer or residuum, and not primarily a result of strict recipe and raw material control. Furthermore, it is demonstrated that possibly two independent melting temperature indicators are correlated, suggesting a factual relationship between melting temperature and melt composition. This evidence is taken to develop a “partial batch melting model” for these early glasses, as opposed to the “total batch melting model” of Mediaeval and early modern glasses. Some archaeological implications of this model are briefly discussed.     

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

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

Chemical composition and colouring agents of Roman mosaic and millefiori glass, studied by electron microprobe analysis and Raman microspectroscopy

About 100 fragments of Roman mosaic and millefiori glass were stylistically attributed to a Hellenistic type, a Ptolemaic and Romano-Egyptian period type and an early imperial period type. Twelve representative fragments were studied by electron microprobe analysis and Raman microspectroscopy. Eleven of them display a Na-pronounced recipe with low K, Mg and P contents, typical for the Roman period. Minor differences in composition are unsystematic, not reflecting the stylistic classification. Ionic colouring agents are Mn³⁺ for violet, Cu²⁺ for light blue, Co²⁺ for deep blue and Fe³⁺ for brown translucent colours. Calcium antimonates, lead antimonate and cuprite are the colourants responsible for white, yellow and red colours, respectively, and additionally serve as opacifiers. Mixing of ionic colouring agents and opacifying colourants led to a more differentiated palette of colours. Pb was used as yellow colouring agent, as a flux material and as a stabiliser for the colourant crystals. The remaining fragment consisting of a K-pronounced but still Na-bearing glass matrix was most likely produced during the Middle Ages or later.     

Iron-57 Mössbauer spectral studies of medieval stained glass

⁵⁷Fe Mössbauer spectral data for six excavated and two simulated medieval stained glass samples are reported. Iron-containing precipitates are observed in the two simulated medieval glasses and are responsible for the amber colour of these samples. The ferrous/ferric ratio of the other samples is dependent on the glass composition and glass making conditions. The green glasses are associated with the presence of both ferrous and ferric iron, the ratio being very similar in three of the glasses studied, while in the purple and emerald green glasses the iron which is constitutionally incorporated in the glass is solely in the ferric oxidation state. The UVvisible spectra of some of the glasses are used to assist in interpretation of the colourant action of iron, and the role of Mössbauer spectroscopy in linking separate glass fragments with a common source is also indicated.     

SAND FOR ROMAN GLASS PRODUCTION: AN EXPERIMENTAL AND PHILOLOGICAL STUDY ON SOURCE OF SUPPLY*

This paper reports the results of an experimental study performed on Campanian littoral sand, together with a careful philological analysis of Pliny's text concerning the production of glass using the above sand in order to verify its suitability. Accurate chemical and mineralogical characterization of sand samples and experimental glasses was carried out, proving the unsuitability of sand for glass production in its original state. Taking into account both the results of the philological analysis of Pliny's text and the mineralogical assemblage of the sand, a new hypothesis regarding Roman glass‐making technology is proposed and tested here. The technology implies the production of ‘quartz‐enriched’ sand by means of selective grindings according to the different degrees of hardness and cleavage of the mineralogical phases. Melting experiments, carried out on treated sand and in the temperature range compatible with Roman technology, yielded a glass with composition similar to those of typical Roman glasses. Therefore, new perspectives on the sources of supply of raw materials, hitherto debated, are opened up.     

THE SECTILIA PANELS OF FARAGOLA (ASCOLI SATRIANO,SOUTHERN ITALY): A MULTI‐ANALYTICAL STUDY OF THE GREEN,MARBLED (GREEN AND YELLOW), BLUE AND BLACKISH GLASS SLABS

Analyses at the Cu–K, Fe–K and Mn–K edge were performed to study the green, marbled (green and yellow), blue and blackish (deep greyish olive green) glass slabs decorating three sectilia panels from the archaeological site of Faragola. Results indicate that all slabs were made by mixing siliceous sand with natron, sometimes probably mixed with small percentages of plant ash. Cu²⁺ and Pb antimonates should be responsible for the opaque green colours. The dark green and yellow portions of the marbled slabs are respectively comparable to the slabs comprising only one of these colours. Cu²⁺ together with Ca antimonates probably produced light blue slabs, whereas cobalt was used to produce dark blue slabs. We consider it possible that the abundance ratio of Fe²⁺/Fe³⁺ and the complex Fe³⁺S^2? would have an effect on the blackish slabs. The contribution of Mn cannot be ascertained even if it could have played a role in darkening glass colour. The comparison between the chemical composition of Faragola samples and several glass reference groups provided no conclusive evidence of provenance; whereas, the presence of a secondary local workshop can be hypothesized.     

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.     

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

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

Chemical analysis of 17th century Millefiori glasses excavated in the Monastery of Sta. Clara-a-Velha,Portugal: comparison with Venetian and façon-de-Venise production

A set of ten Millefiori glass fragments dating from the 17th century, originated from archaeological excavations carried out at the Monastery of Sta. Clara-a-Velha (Coimbra, Portugal), were characterized by X-ray electron probe microanalysis (EPMA), Raman microscopy and UV–Visible absorption spectroscopy. All glasses are of soda-lime-silica type. The use of coastal plant ash is suggested by the relatively high content of MgO, K₂O and P₂O₅, as well as by the presence of chlorine. Tin oxide or calcium antimonate were the opacifiers used in the opaque glasses, cobalt in the blue glasses, copper in the turquoise glasses, iron in the yellow and greenish glasses, and iron and copper were found in the opaque red and aventurine glasses. Based on the concentrations of alumina and silica four different sources of silica were identified, allowing the classification of the glasses into the following compositional groups: low alumina (<2 wt%), which includes a sub-group of cristallo samples with SiO₂ > 70 wt%, medium alumina (2–3 wt%), high alumina (3–6 wt%) and very high alumina (>6 wt%). Comparison with genuine Venetian and façon-de-Venise compositions showed that two fragments are of Venetian production, one of Venetian or Spanish production and the remaining are of unknown provenance. In two fragments the glass of the decoration is probably Venetian or Spanish but the glass used in the body is also of unknown provenance.     

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.     

Characterization of some ancient glass beads unearthed from the Kizil reservoir and Wanquan cemeteries in Xinjiang,China

A total of 33 ancient glass beads unearthed from the Kizil reservoir cemetery and Wanquan cemetery in Xinjiang are studied using Raman spectroscopy, scanning electron microscopy with energy‐dispersive spectrometry (SEM–EDS) and other methods. The detailed study of the glassy matrices, the crystalline inclusions and the microstructural heterogeneities for these glass beads has revealed some valuable information to help in the understanding of their possible manufacturing technology and provenance. At least two different types of glass were present in the two cemeteries. For the first time, antimony‐based colourant/opacifier—for example, Pb₂Sb₂O₇ or CaSb₂O₆—was systematically identified in some beads of plant‐ash type soda–lime glass dated to about 1000–500 bc . The limited number of potash glass beads from the Kizil reservoir cemetery, which were dated to about 500–300 bc , used tin oxide as an opacifier. The diverse resources of the soda–lime and potash glasses indicate the existence of a complex trade network between China and the West much earlier than the Western Han Dynasty.     

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.     

THE ANALYSIS OF SECOND MILLENNIUM GLASS FROM EGYPT AND MESOPOTAMIA,PART 1: NEW WDS ANALYSES*

A recent analytical study by SEM–WDS was carried out on 226 glasses from the Late Bronze Age, analysing each of the glasses for a total of at least 22 elements, the largest such analytical study conducted on these glasses. The aim of the analysis was first to identify which elements were brought in with each of the raw materials and, second, to accurately characterize those raw materials. Since different glassmaking sites in Egypt and the Near East would probably use at least some local raw materials and these raw materials will vary slightly from site to site, this has potential for provenancing the glass. Analysis showed new patterns in the compositions of glass from the various sites and led to new conclusions about the supply of raw materials and personnel for the glass workshops. This forms the basis for further work by LA–ICPMS to be presented in part 2 of this paper.     

Potash - a key raw material of glass batch for Bohemian glasses from 14th-17th centuries?

The aim of this work is to verify or refute hypothesis of existence of basic/universal glass batch: quartz sand: potash: limestone, at a ratio of 2: 1: 1 used in Bohemian glass production since the middle ages onwards and to simulate the preparation of a potassium glass type with the composition used in medieval Bohemia. The chemical composition of Bohemian glass, which incorporated in the proposed glass batch for glassmaking on a laboratory scale, was evaluated by (a) findings directly related to glassmaking (samples from glasswork in Moldava dating back to the 15th century) and (b) information from publications.Experimentally produced glasses for the present paper were prepared from raw materials such as ash, leached ash, potash, limestone and quartz sand. The plant raw materials (spruce, beech and bracken ashes, raw and refined potash) were treated and prepared by methods similar to the production procedures used in the pre-industrial era.The main contrast was found in the CaO/K₂O weight ratio, which was determined in glasses that were characteristic of given periods. While this ratio was often below 1 in glasses of the 15th century, it reached values above 1 in glasses at the turn of the 16th-17th centuries. This result may indicate that the composition of the glass batch had changed.The results of the present study reject the current scholarly work dealing with glass batch composition during the 14th-17th centuries and confirm that glass produced in some Bohemian medieval glassworks could have been melted from a batch that included plant ash, making the use of limestone unnecessary. The traditional suggestion of the exact ratios of raw materials, often cited in historical literature, seems to be impossible. The glassmakers had to react to the variable composition of the raw materials, especially plant ash.     

A comparison of the treatment of errors in radiocarbon dating calibration methods

The application of radiocarbon dating to archaeological samples generally requires calibration of ¹⁴C dates to calendar ages and interpretation of dating errors. In this paper, four recent methods of age calibration are assessed, particularly with regard to their quality of error treatment. Recent experimental research has suggested that commonly quoted errors on “raw” ¹⁴C dates may require enlargement to more realistic levels, which, when incorporated in the calibration schemes, produce a considerable increase in the size of the typical calibrated interval. A general decrease in the sensitivity of ¹⁴C dating using single, “normal precision” dates is implied. Thus typical calibrated age intervals range from 300 to 1300 years (approximate 95% confidence level), with little improvement resulting if “high precision” calibration systems are used to correct “normal precision” dates. Of the four methods considered here, that proposed by Neftel is found to provide the most objective, flexible, comprehensive and “easy to use” scheme. This method is particularly recommended for its treatment of errors both on the dates to be calibrated and on the calibration curve itself.     

GLASS BY DESIGN? RAW MATERIALS,RECIPES AND COMPOSITIONAL DATA*

Compositional analyses of ancient and historic glasses have often been interpreted in terms of the use of specific raw materials in glass manufacture. However, the known inhomogeneity of many glass‐making raw materials and the insolubilities of some compounds make any explanation of compositional data problematic. This paper looks at three glass‐making alkalis with a view to understanding how the compositions of these raw materials are carried through to the final glass. The chemistry and variability of the raw materials are discussed, as is their contribution to the final glass composition. In addition, the choices and decisions made by glassmakers are acknowledged in the final glass compositions. This combination of factors addresses the complexity of predicting the use of specific raw materials from the finished glass composition.