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.     

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.     

ICP–MS ANALYSIS OF GLASS FRAGMENTS OF PARTHIAN AND SASANIAN EPOCH FROM SELEUCIA AND VEH ARDAŠ?R (CENTRAL IRAQ)*

Forty‐one glass fragments were analysed by inductively coupled plasma – mass spectrometry, determining 40 major, minor and trace elements, including rare earth elements. The fragments came from excavations carried out at the archaeological sites of Seleucia and Veh Arda??r in modern Iraq, and were dated to the Parthian and Sasanian epochs. Analytical data indicate that all the samples are silica–soda–lime glasses. Magnesium and potassium oxide contents below 1% suggest that eight out of nine glasses from Seleucia, dating from between the first and the third century ad , could have been obtained by use of an evaporite as a flux; the same conclusion can be drawn for some of the Sasanian glasses dating from the fourth and fifth centuries ad . The other glasses from Veh Arda??r, as well as the remaining sample from Seleucia, are characterized by higher contents of magnesium and potassium, which suggests recourse to plant ash; different magnesium and phosphorus contents allow one to separate these samples into two main groups, pointing to the use of different kinds of plant ash. Aluminium and calcium contents, together with trace element data, may indicate that different sands were used for preparing glasses of different composition. Samples from Seleucia and Veh Arda??r are mainly blue–green and green to yellow–green, respectively; iron and manganese contents suggest that the furnace atmosphere was mainly responsible for the development of these hues.     

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.     

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.     

A STUDY OF GLASS BEADS FROM THE HALLSTATT C–D FROM SOUTHWESTERN POLAND: IMPLICATIONS FOR GLASS TECHNOLOGY AND PROVENANCE*

Eighty‐one samples taken from 68 glass beads found in southwestern Poland on sites of the Lusatian culture from the Hallstatt C and Hallstatt D subphases were analysed by EPMA. A subsample of 18 of these were additionally subjected to analysis by means of LA–ICP–MS in order to validate the results obtained by EPMA. Some glass was made using mineral soda and some using plant ash rich in sodium. Both high‐magnesium soda–lime glass (HMG) and low‐magnesium soda–lime glass (LMG) were identified. A large number of samples are characterized by low MgO content and medium K₂O content (LMMK glass), combined with low concentrations of CaO and high Fe₂O₃ and Al₂O₃. All the LMMK glass contains numerous silica crystals and inclusions composed of a number of elements (most frequently Cu, Co, Sb, As, Ag, Ni and Fe). The LMMK glass was presumably made in Europe during the Hallstatt C.     

A Great Big Melting Pot: Exploring Patterns of Glass Supply,Consumption and Recycling in Roman Coppergate,York*

One hundred and ninety three glass fragments from the canabae in York were analysed (first to fourth centuries). They fall into six compositional groups: antimony colourless (Sb), high‐manganese (high‐Mn), low‐manganese (low‐Mn), mixed antimony and manganese (Sb–Mn), high iron, manganese and titanium (HIMT) and plant ash. Some groups represent production groups, some of which appear to be in limited supply in this western outpost, but are more prevalent elsewhere, and others reflect changing supply mechanisms. The majority of glasses fall into groups that demonstrate extensive recycling of glass. This has important implications for determining provenance using trace elements and isotopes.     

CHALLENGES IN THE ANALYSIS OF HETEROGENEOUS POTTERY BY LA–ICP–MS: A COMPARISON WITH INAA*

Tempers added to pottery have the potential to obscure geographical variation in the chemistry of exploited clay resources when analysed using bulk methods. A pilot study was conducted to assess the possibility of using LA–ICP–MS to analyse clay matrix in pottery with extremely subtle partitions between INAA chemical groups. LA–ICP–MS was used to analyse the clay matrix of 32 pottery samples from seven Middle and Late Woodland period (c. ad 200–800) sites in north‐east Florida and results were compared to data from INAA of the same samples. The results reveal many of the challenges in analysing highly heterogeneous materials with LA–ICP–MS. However, the study also generated data that are potentially useful in the determination of pottery provenance. In some respects, LA–ICP–MS of clay matrix replicated the chemical variation recorded by INAA, and in other respects the results are divergent. The similarities and differences between these results are explained by specific differences between the methods and the materials analysed (matrix versus bulk analysis). Suggestions for improving the method are discussed.     

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.     

DEEPLY COLOURED AND BLACK GLASS IN THE NORTHERN PROVINCES OF THE ROMAN EMPIRE: DIFFERENCES AND SIMILARITIES IN CHEMICAL COMPOSITION BEFORE AND AFTER ad 150*

In this work we attempt to elucidate the chronological and geographical origin of deeply coloured and black glass dating between 100 bc and ad 300 on the basis of their major and trace element compositions. Samples from the western and eastern parts of the Roman Empire were analysed. Analytical data were obtained by means of a scanning electron microscope – energy‐dispersive system (SEM–EDS, 63 samples analysed) and laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS, 41 samples analysed). Among the glass fragments analysed, dark brown, dark purple and dark green hues could be distinguished. Only among the dark green fragments could a clear compositional distinction be observed between fragments dated to the periods before and after ad 150. In the early samples (first century bc to first century ad ), iron, responsible for the green hue, was introduced by using impure sand containing relatively high amounts of Ti. In contrast, a Ti‐poor source of iron was employed, containing Sb, Co and Pb in trace quantities, in order to obtain the dark green colour in the later glass samples. The analytical results obtained by combining SEM–EDS and LA–ICP–MS are therefore consistent with a differentiation of glassmaking recipes, detectable in glass composition, occurring in the period around ad 150.     

The Supply of Glass at Portus Ilicitanus (Alicante,Spain): A Meta‐Analysis of HIMT Glasses

Portus Ilicitanus (Picola, Alicante) was the main sea harbour of the Roman Colonia Iulia Ilici Augusta and as such played a crucial role in the supply of fundamental commodities to the Iberian Peninsula. Excavations yielded large quantities of glass in fourth‐ and early fifth‐century contexts. Elemental analysis of 60 samples by laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS) confirmed that the glasses were imported from the Eastern Mediterranean. A majority of the glasses correspond to the HIMTa primary production group, which originates from Egypt. The statistical evaluation of published data of 589 HIMT glasses further revealed differential distribution patterns of the HIMTa and HIMTb subtypes between the Eastern and Western Mediterranean, suggesting chronological trends that are linked to wider geopolitical changes. This demonstrates the need for systematic large‐scale approaches to identify supply patterns and possible factors underlying geographical differences and/or chronological developments.     

Glass Fragments from the Crypta Balbi in Rome: the Composition of Eighth‐century Fragments

Eighth‐century glass fragments from the Crypta Balbi in Rome were analysed by inductively coupled plasma emission spectroscopy. The samples included fragments of artefacts as well as ingots of raw glass and wasters. All the fragments proved to be soda–lime glasses. Manganese‐to‐iron atomic ratios are highly variable and determine the colour of a large number of samples. Fairly high copper contents, generally associated with relatively high amounts of antimony and lead, were detected in some green and blue–green samples: this suggests recycling of glass in the form of opaque mosaic tesserae. All three elements are higher in eighth‐century than in previously analysed seventh‐century fragments. This may indicate greater recourse to recycled glass, related to a reduction in trade exchanges in the Mediterranean.     

COMPOSITION PROFILES AND TIME EVOLUTION OF BURIED MARBLE PATINAS BY LA–ICP–MS AND LASER‐INDUCED MICRO‐PHOTO‐LUMINESCENCE

The present work aims to study surface composition profiles on buried marbles as well as their time evolution. Fifty samples from gravestones, buried for up to 80 years, were analysed by laser‐induced photoluminescence and LA–ICP–MS. The results include profiles of ²⁵Mg, ²⁷Al, ⁵⁵Mn, ⁵⁷Fe, ⁸⁸Sr and organic complexes of calcium, existing in the marble patina. The depth at which ⁸⁸Sr reaches its bulk value proved to be the best parameter to measure patina thickness. A diffusion model adopted from dissolution studies made on gravestones exposed to the atmosphere was successfully applied to the patina thickness data. The model fails to predict patina thicknesses for ancient excavated objects. However, it seems that ‘Sr alteration depth’ values alone can be used for discriminating ancient from recently buried surfaces.     

DATA ON 61 CHEMICAL ELEMENTS FOR THE CHARACTERIZATION OF THREE MAJOR GLASS COMPOSITIONS IN LATE ANTIQUITY AND THE MIDDLE AGES

Sets of 20 soda ash, 16 soda lime and 23 wood ash glasses mainly from excavations in Europe were analysed by microprobe and LA–ICP‐MS for 61 elements and are presented as average concentrations with standard deviations. Concentrations of sodium, potassium and magnesium allow the major glass type to be identified. Specific compositions of the raw materials of glass production indicate certain sources, technical processes and ages. Heavy minerals etc. of quartz sands contain rare earth elements (REE) from crustal fractionations that are different for the three major glass types. Accumulations of P, B, Ba, Mn and K in wood from soils by organic processes can characterize glass from certain regions.     

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.     

THE PROVENANCE OF OBSIDIAN ARTEFACTS FROM THE WĀDĪ ATH‐THAYYILAH 3 NEOLITHIC SITE (EASTERN YEMEN PLATEAU) BY LA–ICP–MS

The geological sources of obsidian in the Red Sea region provide the raw material used for the production of obsidian artefacts found in prehistoric sites on both sides of the Red Sea, as far afield as Egypt, the Persian Gulf and Mesopotamia. This paper presents the chemical characterization of five obsidian geological samples and 20 prehistoric artefacts from a systematically excavated Neolithic settlement in highland Yemen. The major element concentrations were determined by SEM–EDS analysis and the trace element concentrations were analysed by the LA–ICP–MS method, an almost non‐destructive technique capable of chemically characterizing the volcanic glass. A comparison of archaeological and geological determinations allows the provenance of the obsidian used for the Neolithic artefacts to be traced to definite sources in the volcanic district of the central Yemen Plateau.     

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.     

REPRODUCIBILITY OF ELEMENTAL ANALYSES OF BASALTIC STONE ARTEFACTS BY QUADRUPLE ICP–MS USING DIFFERENT SAMPLE SIZES AND DIGESTION METHODS,WITH IMPLICATIONS FOR ARCHAEOLOGICAL RESEARCH

Using high‐precision inductively coupled plasma mass spectrometry (ICP–MS), we measured >40 elements in basalts sampled by diamond micro‐drills to evaluate the effectiveness of different digestion methods and the reproducibility of elemental analysis for different sample sizes from 5 mg to 100 mg. The results indicate that those elements that are most suitable for geochemical characterization, such as rare earth elements (REE), high‐field strength elements (HFSE) and certain mobile elements (Rb, Sr, Th, U), show excellent reproducibility with an average relative standard deviation (RSD) of 3% between open‐beaker and pressured ‘bomb’ digestion methods. This observation rules out the presence of refractory phases such as zircon, which can only dissolve in pressured ‘bombs’, and suggests that the results from open‐beaker digestion are reliable. The ICP–MS data for powders of different weights ranging from 10 to 100 mg collected from two fine‐grained basalt artefacts display excellent reproducibility, with a RSD of <5% for the most important elements. The reproducibility is reduced when including the 5 mg weight fraction (RSD of ～2–9%), which is still sufficient for archaeological applications. Our results demonstrate the usefulness of 10 mg samples for elemental measurement, which is valuable for geochemical characterization and sourcing of fine‐grained basalt artefacts from museum collections that require minimal destructive sampling.     

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.     

ARCHAEOMETRIC ANALYSES ON ‘CORINTHIAN B’ TRANSPORT AMPHORAE FOUND AT GELA (SICILY,ITALY)*

The aim of this work is to throw light on the archaic production of ‘Corinthian B’ amphorae, which are widely diffused in the Western Mediterranean basin and are also present in Greece, but whose geographical provenance is still under discussion. We analysed a group of 37 samples belonging to different ceramic classes dated to the sixth and fifth centuries bc . In particular, there were 19 sherds of trade amphorae of the so‐called archaic ‘Corinthian B’ type, from archaeological excavations in Gela (Sicily, Italy). As a comparison, we also investigated 18 samples of tiles and local coarse pottery from Sibari (Calabria, Italy). The samples were analysed using different techniques, such as optical analysis with a polarized‐light microscope (OM), X‐ray diffraction (XRD), Fourier transform–infrared absorption (FT–IR) and inductively coupled plasma–optical emission spectroscopy (ICP–OES). The combination of these complementary analytical methods allowed us to characterize the samples, determine their firing temperatures and identify the probable provenance. The study of thin sections of sherds by OM allowed us to divide the investigated amphorae into two main groups: the first was characterized by a composition that suggested a Western provenance, in particular from the Calabrian–Peloritan region; the second one was very similar to the ‘Corinthian B’ amphorae that come from Corinth and have been classified as ‘fabric class 1’ by Whitbread (1995 ). The XRD and FT–IR results permitted us to determine the mineral composition of the findings and to estimate their firing temperature. The ICP–OES technique was particularly useful in identifying the production centres. In fact, in the studied pottery, this analysis revealed Ni and Cr values that were noticeably different between Greek and southern Italian production.