Isotopic Composition of Lead in Copper Ores and a Copper Artefact from the La Profunda Mine (León,Spain)

This paper continues the characterization of the lead isotopic fingerprint of ancient copper mines in the north‐west of Spain. In this work, the lead isotopic compositions found in copper ores from the La Profunda mine are presented. Azurites and malachites sampled from this deposit were subjected to lead isotope analysis by multicollector ICP–MS. The results showed a clear radiogenic lead signature compatible with the presence of uranium‐rich minerals (such as zeunerite) in the same mining complex. Moreover, a rare copper artefact, found in the galleries of the mine during its modern exploitation, was also analysed and showed that local mineral was used for its manufacturing.     

Defining the Lead Isotopic Fingerprint of Copper Ores from North‐West Spain: The El Milagro Mine (Asturias)

This study is focused on the El Milagro mine (Asturias, Spain) and is part of a large‐scale effort on the measurement of the lead isotopic composition of Spanish copper ores from prehistoric mines in the provinces of Asturias and León, from which no data were available until recently. Lead isotopic values are compared to the published lead data from the El Aramo mine in the same region. The results show that both mines have a very similar lead isotopic composition, apart from some highly radiogenic samples in the El Milagro mine, which are clearly different from those previously reported for the Iberian Peninsula.     

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.     

A Multidisciplinary Approach for the Archaeometric Study of Pozzolanic Aggregate in Roman Mortars: The Case of Villa dei Quintili (Rome,Italy)

This contribution focuses on the study of historical mortars from a Roman archaeological site known as Villa dei Quintili, a monumental villa located in the south‐eastern part of Rome (Italy). The study was carried out on 38 mortar samples, collected from several edifices within the complex. A multi‐analytical approach, including polarized optical microscopy, scanning electron microscopy coupled with energy‐dispersive system and laser ablation inductively coupled plasma mass spectrometry, was used to analyse the pozzolanic material used for the preparation of mortars. Data obtained on both major and trace elements were compared with the compositions of Pozzolana Rossa, Pozzolana Nera and Pozzolanella samples from the Alban Hills volcanic district, collected from a historic quarry nearby, as well as with literature data. The results of such a multidisciplinary approach allowed us to recognize the use of all three pozzolan types for the aggregate fraction of examined mortars from the Villa dei Quintili.     

Smelting and recycling evidences from the Late Bronze Age habitat site of Baiões (Viseu,Portugal)

Many aspects of bronze production during Late Bronze Age in Western Europe are so far unknown. In the present study selected artefact fragments and metallurgical debris, which include a slag fragment, from the emblematic Late Bronze Age habitat site of Castro da Senhora da Guia de Baiões (Viseu, Portugal) have been studied by optical microscopy, micro-EDXRF, SEM–EDS and XRD. Evidences were found for bronze production involving smelting and recycling. Compositional analysis showed that the artefacts are made of a bronze with 13 ± 3 wt.% Sn (average and one standard deviation) and a low impurity pattern, namely <0.1 wt.% Pb, being comparable with the composition of other bronzes from the same region (the Central Portuguese Beiras). This alloy is generally different from elsewhere Atlantic and Mediterranean bronzes, which show frequently slightly lower Sn contents and higher impurity patterns, namely Pb which is often present as an alloying element. The present study gives further support to early proposals suggesting the exploration of the Western Iberian tin resources during Late Bronze Age, and besides that, it indicates that metalworking and smelting could have been a commonplace activity requiring no specific facilities, being bronze produced at a domestic scale in this Western extreme of Europe.     

Compositional Analyses of Mortars from the Late Antique Site of Son Peretó (Mallorca,Balearic Islands,Spain): Archaeological Implications

The paper presents the mineralogical, petrographic and chemical analyses of mortars from an Early Christian complex found in Mallorca (Balearic Islands) and dated to between the fifth and the eighth centuries ad . We characterized several mortars found at the site, in order to gather information on the raw materials used, as well as on the technology of production, and similarities among the samples. The analyses were aimed at solving specific archaeological questions regarding the building phases of the site and, in particular, the synchronic or diachronic presence of two baptismal basins in the same Christian complex.     

Technical Studies on the Bronze Age Metal Artefacts from the Graveyard of Deh Dumen,South‐Western Iran (Third Millennium BC)

During the excavations of the graveyard at the site of Deh Dumen in south‐western Iran, 15 graves from the Early/Middle Bronze Age were uncovered that contained a variety of metallic artefacts. This paper reports on the analysis of nine metal artefacts, including eight broken vessels and a decorative strip that covered the handle of a dagger. The ICP–MS results showed that the bodies of the vessels are made of tin bronze alloy with variable amounts of tin, while the internal piece of the base of one vessel is made from an arsenical copper alloy. Further, the metallic strip is a thin sheet manufactured with partially pure silver. Microanalytical and microstructural information yielded by SEM–EDS revealed elongated Cu–S inclusions and lead globules as various phases formed in bronze solid solution. This study presents some information about the transition from arsenical copper to bronze metallurgy in the third millennium bc in south‐western Iran.     

COOKING AND PAINTED WARE FROM SAN GIUSTO (LUCERA,FOGGIA): THE PRODUCTION CYCLE,FROM THE SUPPLY OF RAW MATERIALS TO THE COMMERCIALIZATION OF PRODUCTS*

Archaeological excavation at the San Giusto site (Lucera, Italy) has unearthed a Late Antique kiln that was most certainly dedicated to the production of cooking ware. An archaeometric study of numerous specimens of cooking and painted ware found at this site was carried out using optical microscopy, scanning electron microscopy, micro‐Raman spectroscopy, X‐ray diffraction, X‐ray fluorescence, inductively coupled plasma mass and optical emission spectrometry and instrumental neutron activation analysis. The integration of historical–archaeological data with archaeometric data has revealed that these specimens can be attributed to the San Giusto site. Furthermore, the production cycle of this ware can thus be reconstructed: from the diversified supply of raw materials (fluvial and marine sediments), to the relatively complex preparation of the paste, to firing at variable temperatures (600–750°C for cooking ware; 850–1050°C for painted ware).     

New Data on the Exploitation of Obsidian in the Southern Caucasus (Armenia,Georgia) and Eastern Turkey,Part 1: Source Characterization

A large analytical programme involving both obsidian source characterization and obsidian artefact sourcing was initiated recently within the framework of the French archaeological mission ‘Caucasus’. The results will be presented in two parts: the first part, this paper, deals with the presentation and characterization of obsidian outcrops in the southern Caucasus, while the second presents some results obtained from a selection of artefacts originating from different Armenian sites dated to between the Upper Palaeolithic and the Late Bronze Age. The same analytical method, LA–ICP–MS (laser ablation inductively coupled plasma mass spectrometry), has been used to characterize all the studied samples (both geological and archaeological). This method is more and more widely used to determine the elemental composition of obsidian artefacts, as it causes minimal damage to the studied objects. We present in this first part new geochemical analyses on geological obsidians originating from the southern Caucasus (Armenia, Georgia) and eastern Turkey. These data enhance our knowledge of the obsidian sources in these regions. A simple methodology, based on the use of three diagrams, is proposed to easily differentiate the deposits and to study the early exploitation of this material in the southern Caucasus.     

Fuel Efficiency of Ancient Copper Alloys: Theoretical Melting Thermodynamics of Copper,Tin and Arsenical Copper and Timber Conservation in the Bronze Age Levant*

The melting of pure or alloyed copper, tin and arsenical copper ingots or recycled objects was a drain on the timber and dung fuel resources of many cultures. This paper suggests formulae grounded in thermodynamic principles in an attempt to estimate the energy requirements necessary to melt copper alloys common to both Old and New World cultures, with the goal of identifying consumption and conservation patterns. It has been suggested that tin bronze metallurgy was first adopted in the Levant during the Early Bronze Age (EB) IV, at the onset of the Late Holocene climate episode (c.2300–2000 bc ), becoming the most desired alloy by the Middle Bronze Age (MB) II (2000–1530 bc ) due to the ease of melting tin. To test this hypothesis, the formulae are applied here to all published Levantine EB IV – MB II copper alloys. Fuel conservation rates are proposed based on the thermodynamic formulae. Tin bronze is demonstrably more fuel efficient than pure copper. Due to the inherent difficulties in predicting the behaviour of arsenical copper compounds, it is suggested that melting experiments with representative alloys are conducted to further test and refine these energy relationships.     

CUERDA SECA CERAMICS FROM AL‐ANDALUS,ISLAMIC SPAIN AND PORTUGAL (10TH−12TH CENTURIES AD): INVESTIGATION WITH SEM–EDX AND CATHODOLUMINESCENCE*

Since little is known about the cuerda seca technique, our aim has been to complete an initial analysis of 11th‐century cuerda seca by studying fragments from the 10th century (Pechina, Almería) and the 12th century (Mértola and Almería), so as to establish the diachronic evolution of this technique. Characteristics specific to cuerda seca ceramic glazes were investigated using scanning electron microscopy (SEM) and quantitative chemical analysis with energy‐dispersive X‐ray spectrometry (EDX). The chemical compositions of the different‐coloured glazes (green, black, yellow and white) have given us valuable indications about the evolution of the technique. The opacification mode and the firing process were also investigated. With the help of cathodoluminescence (CL) and the study of modern ‘cuerda seca’ glazed ceramics, new hypotheses regarding the number of firing stages, taking into account glaze and paste transformations and their interactions, are put forward.     

Oil Lamps from the Catacombs of Canosa (Apulia,Fourth to Sixth Centuries AD): Technological Features and Typological Imitation

Fifty oil lamps from the catacombs of ‘Ponte della Lama’ (Canosa di Puglia, second to sixth centuries ad ) were analysed to understand the correlations existing between types and fabrics and to determine their provenance. Petrographic and chemical analyses confirmed the archaeological hypothesis of local production of the oil lamps, using fluvial deposits. However, the three samples of oil lamps imitating the African ‘Atlante VIII’ are considered chemical outliers compared to the rest and are supposedly of foreign origin. The extensive and original repertory of lamp types characterizes Canusium as the production centre in the late Roman period.     

Obsidian from Pulo di Molfetta (Bari,Southern Italy): provenance from Lipari and first recognition of a Neolithic sample from Monte Arci (Sardinia)

Twenty-four obsidian artefacts of the Neolithic Age were found at the large karstic doline of Molfetta (near Bari) along the Southern Italian Adriatic coast. Non-destructive chemical analyses of the glass, by SEM-EDS, allowed their source rock regions to be determined. Twenty-three of the studied artefacts had been traded from the island of Lipari. Only one sample had a glass composition and microphenocrysts (biotite, pyroxene and feldspar) that indicate provenance from the Monte Arci area of Sardinia, in particular from the Perdas Urias (SC) outcrops. The attribution of this artefact to Sardinia enlarges the geographical pattern of Monte Arci obsidian exploitation and distribution from island to Southern Italy during the Middle to Late Neolithic.     

Preliminary Characterization of Pottery by Cathodoluminescence and SEM–EDX Analyses: An Example from the Yeha Region (Ethiopia)

Yeha was a political and cultural centre of the Ethio‐Sabaean culture (D’MT) in northern Ethiopia and southern Eritrea. Part of the archaeological research deals with pottery of local, regional and imported origin. The research—investigations and examinations—tries to classify local pottery in two ways: first, by analysing the mineralogy of the temper using light microscopy and cathodoluminescence; and, second, by analysing the main element composition of the clay matrix using a scanning electron microscope with energy‐dispersive X‐ray detection (SEM–EDX). The cathodoluminescence shows that the temper material has differences in the colours of feldspars with a similar mineralogical composition. The results demonstrate that the pottery was produced by using local material that originates from various sources in the Yeha region and that the same raw materials were used in different types of pottery.     

Never Judge A Gold Object by Its Surface Analysis: A Study of Surface Phenomena in a Selection of Gold Objects From the Staffordshire Hoard

With the introduction of commercially available handheld XRF analysers, there is a growing problem that the results, simply taken at face value, are regarded as representative of the bulk gold alloys of the objects analysed in museums and used for treasure analysis. It is well known that surface analysis is problematic, and the aim of this study was to test whether non‐destructive surface analysis could be useful in grouping the very large numbers of fragmentary pieces in the Anglo‐Saxon Staffordshire Hoard. Surface and subsurface analyses of 16 objects from the Hoard were carried out by X‐ray fluorescence (XRF) and scanning electron microscopy with energy‐dispersive X‐ray analysis (SEM–EDX). The results indicate that there are significant but inconsistent levels of enrichment of the gold at the surface of many of these objects, due to the loss of both copper and silver. The significant loss of silver (up to 50% relative in some cases) suggests that some form of deliberately induced depletion gilding was carried out during manufacture to remove both silver and copper from the surface. In three cases, an increase in silver at the surface compared to the core metal was detected: this might tentatively be explained by redeposition from contact with silver objects during burial. These results have clear implications for the reliability and interpretation of surface analysis data of gold alloys from this period.     

Obsidian Sources in the Regions of Erzurum and Kars (North‐East Turkey): New Data

The obsidian sources on the Erzurum–Kars Plateau have not been extensively surveyed, and their geochemical signatures are still poorly understood. Yet a significant number of artefacts from archaeological sites in Georgia and Armenia have produced chemical compositions that are unrelated to any Turkish or Caucasian source analysed so far. Their origins may lie in these poorly known deposits. The objective of the collaborative project undertaken by the University of Erzurum and the French mission ‘Caucasus’ is to study the sources of obsidian in the Erzurum and Kars regions, in order to shed light on the intensity of exploitation of this material, and to highlight the exchange networks that may have existed between north‐eastern Turkey and the southern Caucasus. The analyses that we have carried out on the samples taken during this exploratory survey have enabled a definite extension of the territory of circulation of this obsidian to western Transcaucasia. The lack of knowledge concerning the diffusion of obsidian from the regions of Erzurum and Kars thus appears for the moment mainly related to insufficient geochemical characterization of the sources, confirming the importance of future surveys.     

Plasters from Different Buildings of the Sacred Precinct of Tenochtitlan (Mexico City): Characterization And Provenance

In this work, we present the results of the characterization of 20 lime plaster samples taken from the Sacred Precinct of Tenochtitlan (Mexico City), the ancient capital of the Aztec empire. The samples come from different buildings of this precinct (A, B and D) and from the west façade of phase VI of the Templo Mayor pyramid. The objective of the work is to characterize the plaster samples, to understand the raw materials used, and to evaluate the presence of similarities and differences among the samples in the building techniques and raw materials employed. All the samples were studied with OM, SEM–EDS and LA–ICP–MS. The study provided evidence of the plastering and replastering practice in the same constructive phases. The results of the analyses showed the existence of important similarities and differences among buildings and constructive phases in the Sacred Precinct. In order to understand the provenance of the limestone used in the plasters, the lumps and the binder of the samples were analysed. The results were compared with those of the limestone outcrops located in central Mexico. The provenance study showed that all the limestone used in the construction of the analysed buildings of Tenochtitlan's Sacred Precinct comes from the Tula region.     

Provenance Analyses of the Volcanic Rock Grinding Stones from the Greek Colony of Selinunte,Sicily (Italy)—Constraints and Possibilities

The petrography as well as the major and trace element compositions of the Selinunte grinding stones, made of grey vesicular lava, were analysed. By comparison with geochemical data from volcanic rocks in the Mediterranean, we were able to determine that only a minor number of the tools were extracted from the nearest volcanics of Mount Etna and the Hyblean Mountains, while the majority of the grinding stones were most probably imported from the Aeolian Islands, although an origin from the Aegean cannot be excluded entirely. The results are important in order to scrutinize trading connections, especially for the earlier times of settlement during the sixth century bc .     

Archaeometric investigation of Roman tesserae from Herculaneum (Italy) by the combined use of complementary micro-destructive analytical techniques

Vitreous tesserae from two mosaics in Herculaneum (Italy) dating from the 1st century AD have been investigated in order to gather information on Imperial Age opaque glass. The combined use of complementary micro-destructive analytical techniques, namely optical microscopy (OM), scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS), inductively coupled plasma-mass spectrometry (ICP-MS), transmission electron microscopy (TEM), and X-ray powder diffraction (XRPD) allowed to define the nature of formers, fluxes, chromophores and opacifying compounds and to determine the type of raw materials employed for their introduction. The results confirmed the high technological level of Imperial Age glassmakers and clarified some details of the production processes. Experimental data have been obtained concerning formation of antimony-based opacifiers. The presence of tin-containing Ca- and Pb-antimonates has been ascertained in various green, yellow and turquoise tesserae. Moreover, unusual divergences from the established Roman age ‘low magnesia–low potash’ (LMLK) glass composition have been found for some red and green samples.     

Preliminary neutron diffraction study of two fenestrated axes from the ‘Enot Shuni' Bronze Age cemetery (Israel)

Neutron diffraction (ND) analyses of ancient metals show that this method is capable of detecting differences in the inner composition and microstructure of ancient metal objects. Here, ND measurements were conducted on two ‘eye shaped’ axes from the end of the 3rd-beginning of the 2nd millennium BC. The objects were excavated from the ancient cemetery of ‘Enot Shuni' Israel; one is made of bronze and the other of silver. Both artefacts are rare finds, with the silver axe unique in the archaeology of Israel, and therefore had to be analysed locally. For that purpose, a newly assembled diffractometer (KARL) at the IRR-1 of the Nuclear Research Centre (Soreq, Israel) was used. ND measurement on the bronze axe revealed the existence of an α-phase with a range of Cu/Sn ratios (Cu–Sn solid solutions) and some amount of a δ-phase (intermetallic compound of Cu and Sn). The silver axe ND pattern shows the existence of an α-phase (Ag–Cu solid solution) and some amount of copper metal. Our ND data are discussed in comparison with XRF surface measurements and thermal neutron radiography. The results are shedding more light on the in-depth material composition profile, as well as on the objects’ structural and compositional affinities, and help to better understand the production processes and assist in conservation decisions.