Provenance Determination Research Articles

Antimony as a raw material in ancient metal and glass making: provenancing Georgian LBA metallic Sb by isotope analysis

ABSTRACT Sb was frequently used as a raw material, both in ancient glass-making (as an opacifier and decolouriser) and metallurgy (either as an alloying element or as a pure metal). Despite this ubiquity, antimony production has only occasionally been studied and questions concerning its provenance are still not satisfactorily answered. This study evaluates the suitability of Sb isotope analysis for provenance determination purposes, as experiments under lab conditions have revealed fractionation occurring during redox processes in oxidising stibnites and in making opacified glasses. The results of this paper help to evaluate the possible influence of the pyrotechnological processes on the antimony isotope composition of glass artefacts. This paper focuses on the Caucasus as case study by applying mineralogical, geochemical and isotopic analysis to Georgian ores (mainly from the Racha-Lechkumi district) and Late Bronze Age (LBA; 15th–10th century BCE) metallic Sb objects found at the sites of Brili and Chalpiragorebi.

International Pots of Mystery: Using PXRF spectroscopy to identify the provenance of botijas from 16th Century sites on Peru's north coast

This study presents the results of visual and portable X-ray fluorescence (PXRF) analyses of botijas/olive jars from the 16th Century sites of San Miguel de Piura and Carrizales, north coast Peru. Although visual analysis generally enabled the discrimination of Spanish- from New World-made sherds, PXRF analyses permitted further provenance determinations to specific regions and countries of origin. The results show that botijas from these sites variously derive from Spain, Panama and South America, with only Spanish sherds present at the church contexts under study in San Miguel de Piura. At Carrizales, Spanish botijas are abundant across church and domestic associated spaces, with only slightly higher concentrations recovered from church-affiliated contexts, and Panamanian and South American sherds also present. These results suggest that numerous economic, socio-religious and political factors were at play in the use and potential re-use of botijas at these sites.

Color and painting techniques in Etruscan architectural slabs

In 2016, a huge amount of archaeological materials, mainly painted architectural slabs, were taken back in Italy from the Carlsberg Glyptotek of Copenhagen and from the collection of a Swiss art dealer after an investigation of Italian authorities on the illegal antiquities trade. According to style and typology, part of these materials are supposed to come from the UNESCO archaeological site of ancient Caere (Cerveteri); actually, the site was an important Etruscan center where the tradition of painted architectural slabs is attested with a relevant production from the second half of the VI century B.C. Overall, the corpus consists in 1779 fragments grouped in fourteen slabs, turning in homogenous figurative scenes and exhibiting a polychrome decoration. Due to the fragmentary nature of documentation related to these artefacts, relevant questions on attribution, provenance determination and authenticity of them are currently opened among archaeologists and scientists. A non-destructive analysis campaign was therefore performed by portable XRF and Raman instrumentations with the aim to characterize pigment layers and support the interpretative analysis, in the lack of a proper literature references on raw materials and manufacture technology; moreover, XRD and micro-Raman spectroscopy were carried out on micro-samples to go deeper inside in the material characterization. The multi-analytical investigation allowed to open interesting questions on color palette and painting techniques. A recurrent use of the same pigments was evidenced through the corpus, even with some differences especially in the black pigment layers; the different figurative motifs allowed to classify the fragments in several groups, possible related to as much as different artistic phases, use and/or manufacture centers. Actually, complementary investigation on bulk were performed to unveil possible correlation between figurative cycles and provenance sites. Comparative studies with reference materials from Cerveteri area were also performed, providing clues for a discussion on their authenticity.

Materials and provenance determination of lacquerware from the Ryukyu Kingdom period by pyrolysis-gas chromatography/mass spectrometry and 87Sr/86Sr isotope ratio

Three wood chips found in a wooden coffin discovered in the Mumujyana graves of the Ryukyu Kingdom period were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and the 87Sr/86Sr isotope ratio of one piece was measured by multi-collector inductively coupled plasma mass spectrometry to determine the materials used to produce the lacquerware and their provenance. Results from the derivative Py-GC/MS indicate that the lacquer was produced from sap of both Toxicodendron vernicifluum, which grows in eastern Asia, and Toxicodendron succedaneum, which grows in southeastern Asia. The 87Sr/86Sr isotope ratios of the film layer and wooden base of one large chip, which is considered to be a stripped piece of the wooden coffin, were <0.710. The Sr concentration of the film layer, however, was 35.0 ppm, significantly higher than that of raw lacquer sap. It is possible that the Sr isotope ratios of the film layer reflect that of a black pigment observed by cross-section analysis. From the 87Sr/86Sr ratios of two parts of the chip, it is likely that the lacquer painting was done where the black pigment and wood were available. It is likely that the wooden coffin was constructed on the main islands of Japan. Meanwhile, the presence of a chip lacquered with Toxicodendron succedaneum demonstrates that the Ryukyu Kingdom had diverse trade relationships with surrounding countries.

Marble decoration of the Roman theatre of Urvinum Mataurense (Urbino, Marche region, Italy): An archaeological and archaeometric multi-method provenance study

Abstract This paper presents the results of the characterisation, provenance determination, quantification (by count and weight) and contextualisation of the white and coloured marbles used for decorating the Roman theatre of Urbino (Marche region, Italy). The main goals of the paper are to contribute to a better understanding of the trade and use of marble in the region of central Adriatic Italy in Roman times, and to demonstrate the socio-cultural importance of architectural decor in Roman society, especially through comparison of the Urbino case with contemporary theatres in the Western Mediterranean. Macroscopic characterisation of white and coloured marbles was followed by thin section petrography, X-ray diffraction and stable isotopic analysis (∂18O and ∂13C) for eight marble samples. In total, twenty-six marble varieties have been identified in the Urbino theatre assemblage. Mineralogical-petrographic and archaeometric analysis shows the presence of white marbles from Carrara (Italy) and Proconnesos (Asia Minor), and greco scritto from Hasancavuslar (Ephesos, Turkey). Coloured marbles, mainly africano, breccia di sciro, breccia medicea, cipollino verde, pavonazzetto and giallo antico, as well more prestigious lithotypes as granito misio, porfido rosso and serpentino, can be traced back to Italy, Greece (mainland and Aegean islands), Asia Minor, Egypt and North Africa. Particularly important is the earliest Roman in situ identification of breccia medicea. Compared to other Roman theatres in the Western Mediterranean, the Urbino theatre stands out for the sumptuousness of its marble renovation, especially in terms of the number of marble varieties. Like other Roman towns in central Adriatic Italy (e.g. Suasa, Trea and Urbs Salvia), Urvinum Mataurense shows a strong integration in the Roman Mediterranean marble trade, with a clear connection with the Greek/Eastern world.

Provenance determination of prehistorical pottery from Oshima Island belonging to Izu islands (Tokyo, Japan) using X‐ray fluorescence spectrometry

A total of 41 pottery shards originating in the Jomon period (14000–300 BC) and Yayoi period (300 BC–250 AD) were excavated from the Shimotakabora site on Oshima Island of the Izu islands (Tokyo, Japan). X‐ray fluorescence spectrometry was used to determine the chemical composition (10 major oxides and 12 minor elements) of the potteries to identify the potteries' provenance, that is, local or nonlocal product. The calibration curves were drawn by synthetic standards prepared from a mixture of chemical reagents containing analytes, which presented good accuracy and reproducibility by analysis of the geochemical references. The pottery samples were classified by multivariate statistics such as principal component analysis and cluster analysis based on their chemical composition. Additionally, the X‐ray fluorescence results were compared with geochemical data from Oshima Island using scatter diagrams. The pottery provenance was identified by their classification. This provenance estimation indicates that 37 of the 41 potteries were brought to Oshima island from Japan's main island, Honshu, in the prehistoric age.

Calcite alabaster artifacts from Hierapolis in Phrygia, Turkey: Provenance determination using carbon and oxygen stable isotopes

AbstractAlabastro fiorito or listato, a vividly colored and strongly patterned carbonate stone, is widely diffused in the ancient city of Hierapolis in Phrygia (Turkey) as building material. This stone, also known as Hierapolis alabaster, was extensively quarried in antiquity in the territory near the city. Numerous ancient quarries of the Hierapolis alabaster were documented in previous studies in sites immediately around the city and also about 13 km northwest of Hierapolis, near Gölemezli. Carbon and oxygen stable isotopes and X‐ray diffraction (XRD) analysis were used to investigate the possibility to discriminate different quarries or different geographically coherent extraction areas; these techniques were also applied to analyze alabaster artifacts from some monuments of Hierapolis as a case study. The data show that carbon and oxygen isotopes may be effective at distinguishing between the quarries of Gölemezli and Hierapolis, and allow for attribution of unknown alabaster artifacts to one of these areas. The possibility to identify the provenance of unknown alabasters from the different extraction sites or geographically coherent extraction areas near Hierapolis using isotopes only is difficult; in some cases XRD analysis to detect aragonite versus calcite may improve the discrimination among Hierapolitan quarries and contribute to the assignment procedure.

Enhancing Understanding of the Emergence of Global Trade: Analysis of 17th‐ to 19th‐Century Spanish Coins Recovered from Western Australian Shipwrecks Using Laser Ablation – Inductively Coupled Plasma – Mass Spectrometry (LA–ICP–MS)

This research uses legacy data from shipwrecks to further our understanding of global silver movement in the 17th to 19th centuries by analysing a collection of silver coins held by the Western Australian Museum. Three hundred and eighty‐nine silver coins were analysed for their trace element fingerprint in order to identify provenance. The coins are a selection from the ships Batavia, Vergulde Draeck, Zuytdorp, Rapid and Correio da Azia, all wrecked off the coast of Western Australia between 1629 and 1816. Analysis was undertaken using laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS), a relatively non‐destructive technique with a sensitivity of parts per million to parts per billion. Data were interpreted using linear discriminant analysis (LDA), which allowed the coins of known provenance to be sorted into identifiable subgroups on the basis of their trace and minor elemental fingerprints, while 27 unidentified coins were compared with this database and their mint of origin predicted. These results have implications for the provenance determination of archaeological artefacts of many materials.

Petrography and mineralogy of the white marble and black stone of Göktepe (Muğla, Turkey) used in antiquity: New data for provenance determination

The discovery near Göktepe (Muğla province, Western Turkey) of an ancient quarrying site of white marbles and black stones has recently been reported by some authors. Assigning the provenance of stone from ancient artifacts to Göktepe is currently possible mainly thanks to chemical, EPR and MGS data. Petrographic description, which many researchers use to characterize ancient marbles, is still incomplete. Several thin sections of both types of stone were thus examined in this study, and also used for cathodoluminescence analysis. As the rock is >99% calcite, trace minerals could only be detected in some samples by XRD analysis of insoluble residues after acetic acid attack. Data on strontium and manganese contents and carbon and oxygen isotopes were also recorded, for better understanding of some petrographic features.A new method of grain size characterization was tentatively introduced to improve the description of grain size variability in the white marble. Microstructure and grain size measurements on thin sections of this marble identify two petrographic varieties: the first is extremely fine with signs of dynamic recrystallization, and the second exhibits texture and MGS similar to those of Carrara marble.Statuary samples of white marble from Villa Adriana (Tivoli, Rome), preliminarily assigned in a previous study partly to Carrara and partly to Göktepe quarry, are reconsidered here.A certain degree of variability was found in the structures and textures in the thin sections of the Göktepe black stone. It may have undergone transformations at an advanced stage of diagenesis. One important source of this variability seems to be a fluid alteration event, revealed by both isotopic and chemical data and trace mineral assemblages.

How much is known about glassy materials in Bronze and Iron Age Italy? New data and general overview

Knowledge of glass trading in protohistoric Southern Italy has been limited by a lack of archeometrical data available to date, preventing comparison with the well-known Northern Italian context. The aim of the present work is to help fill the data gap for Southern Bronze-Iron Age vitreous items and enable a general overview of protohistoric Italian glass supply routes. The paper presents physical-chemical data for 61 vitreous items from 11 Southern Italian sites, dated from the beginning of the Bronze Age up to the Archaic period (22nd–6th century BC), ensuring a complete diachronic analysis. SEM-EDS, EMPA, LA-ICPMS, and XRD analyses permitted definition of the raw materials and manufacturing techniques employed, as well as determination of item provenance. The sample set exhibits great variability of glass chemical types, including plant ash glass, mixed alkali, and natron samples. A complex picture emerges, mostly as regards the different natron glass typologies (High-Zr, Low-Zr, Black, etc.) and their rapid technological evolution in the early 1st millennium BC. Taking into account the data reported in this study and those available in literature for both Northern and Southern Italian Bronze-Iron Ages items, this work demonstrates the existence of different trade routes for the first time. This is especially true for the Early/Middle Bronze Age periods, with Northern Italy involved in trade with Central Europe, and South already involved in Mediterranean trade circuits.

Archaeometric characterization and provenance determination of sculptures and architectural elements from Gerasa, Jordan

This study aims at the identification of the provenance of white marble sculptures and architectural elements uncovered from the archaeological site of Gerasa and neighboring areas, north Jordan. Most of the marbles are probably of the Roman or Byzantine periods. Optical microscopy, X-ray diffraction, and mass spectrometry were used to investigate petrographic, mineralogical and isotopic characteristics of the samples, respectively. Analytical results were compared with the main reference databases of known Mediterranean marble quarries exploited in antiquity. The collected data show that the most likely main sources of the sculptures were the Greek marble quarries of Paros-2 (Lakkoi), Penteli (Mount Pentelikon, Attica), and Thasos-3 (Thasos Island, Cape Vathy, Aliki); the Asia Minor marble quarries of Proconessus-1 (Marmara) and Aphrodisias (Aphrodisias); and the Italian quarry of Carrara (Apuan Alps). Similarly, the Asia Minor quarries of the fine-grained Docimium (Afyon) and the coarse-grained Proconessus-1 (Marmara) and Thasos-3 are the most likely sources of the architectural elements. The results agree with published data on the wide use of these marbles for sculpture and architectural elements.

Archaeometric analysis for provenance and content of roman amphorae from the site of SA mesquida (Mallorca, Spain)

This paper presents the results of an inorganic and organic approach to Roman amphorae found at the rural Roman site of Sa Mesquida (Mallorca). A set of amphorae were discovered in some rooms of the earlier phases of the villa. These amphorae were assigned to a general Tarraconensian and Italic provenance on a macroscopic level. In order to verify this and to accurately determine the provenance an archaeometric characterization was carried out on twelve amphorae. The analytical approach combined wavelength dispersive X-ray fluorescence (WD-XRF) for the chemical analysis, as well as powder x-ray diffraction (XRD) and optical microscopy by thin-section analysis (OM) for the mineralogical and petrographic characterization. In addition, organic residue analysis by gas-chromatography mass spectrometry (GC-MS) was applied to investigate the content of some of the amphorae for which wine was suggested on an archaeological basis. The results have allowed for a better provenance determination identifying some amphorae from specific workshops or micro-regions within ancient Tarraconensis, as well as a better definition of the Italic materials. The organic analysis has confirmed the presence of wine in the analysed samples.

Technology and Provenance Analysis of Glass Fragments from an Ottoman Bathhouse (Hamam) in Kyparissia, Peloponnese, Greece

ABSTRACTThis study focuses on the analysis of a post-medieval assemblage of glass vessels and tableware, recovered from an Ottoman bathhouse in Kyparissia, SW Peloponnese, Greece. The chemical composition of the samples was estimated using SEM/EDS, whereas minor and trace elements were identified by qualitative XRF analysis. Raman spectroscopy was applied in order to examine the connectivity of the silicate glass matrix in more detail. The acquired data indicate significant chemical variations among the samples, especially in regards to the alkali source and the decolourant used. Moreover, one high-lead glass has also been identified. The provenance analysis, which was based on the statistical treatment of the resulted and published analytical data, indicated that the different glass types originated both from the eastern regions of the Ottoman Empire and from glassmaking centres in central and northern Europe. The determination of technology and provenance of the assemblage provided with valuable new information regarding the production and trading network of glass in mainland Greece during the Ottoman rule.

Methodologies for the investigation of corroded iron objects: examples from prehistoric sites in South-eastern Arabia and Western Iran

ABSTRACTAncient iron objects from early Iron Age archaeological sites are almost always severely corroded, which can severely limit the possibilities for their archaeometallurgical analysis. In this paper, a range of corroded iron objects from different sites and regions of the ancient Near East are investigated with the purpose of developing an integrated scientific approach to the investigation of such materials, outlining the capabilities and major technical limitations of currently available techniques. Specific objectives of the research include: (1) Assessing the state of degradation of ancient ferrous objects in respect to the portion of remnant carburized areas preserved; (2) Identifying metallographic structures and evaluating the carbon content from the observation of remnant carburized areas; (3) Developing an understanding of the representativeness of remnant carburized areas in corroded ferrous samples; and (4) Exploring the validity and technical constraints of SEM-EDS analyses of slag inclusions in corroded iron artefacts for the determination of provenance.

Tracking trachyte on the Roman routes: Provenance study of Roman infrastructure and insights into ancient trades in northern Italy

AbstractRoman colonization of northern Italy during the late Republican Age brought about significant building activity in the newly acquired territories, involving the construction of new infrastructure that demanded large amounts of stone. Trachyte of the Euganean Hills was among the most commonly used materials for building roads, bridges, forum squares, and aqueducts. This paper addresses the recognition of the provenance quarry of Euganean trachyte used in Roman public infrastructure in northeastern Italy. Petrographic features and major‐ and trace‐element composition of bulk rock and phenocrysts, analyzed by X‐ray fluorescence (XRF) and laser ablation inductively coupled plasma mass spectrometry (LA‐ICPMS), were used as provenance tracers. The provenance determinations allow for exploring the commercial, political, and economic dynamics involving the supply of trachyte for public works, and the management of Roman quarries, which likely were in competition with each other and separately controlled by the most important nearby cities. Finally, broad insights into ancient trades in northern Italy and the main routes of stone distribution are discussed: most transport was done by ship, being more rapid and less costly, taking advantage of the Adriatic Sea, the Po River, and the many waterways close to the Euganean quarries.

U-Pb detrital zircon dates and provenance data from the Beaufort Group (Karoo Supergroup) reflect sedimentary recycling and air-fall tuff deposition in the Permo-Triassic Karoo foreland basin

Detrital zircon U-Pb age dating was used for provenance determination and maximum age of deposition for the Upper Permian (upper Teekloof and Balfour formations) and Lower Triassic (Katberg Formation) lithostratigraphic subdivisions of the Beaufort Group of South Africa's Karoo Basin. Ten samples were analysed using laser ablation - single collector - magnetic sectorfield - inductively coupled plasma - mass spectrometry (LA-SF-ICP-MS). The results reveal a dominant Late Carboniferous-Late Permian population (250 ± 5 Ma – 339 ± 5 Ma), a secondary Cambrian-Neoproterozoic (489 ± 5 Ma to 878 ± 24 Ma) population, a minor Mesoproterozoic (908 ± 24 Ma to 1308 ± 23) population, and minor occurrences of Devonian, Ordovician, Proterozoic and Archean zircon grains. Multiple lines of evidence (e.g. roundness and fragmentary nature of zircons, palaeo-current directions, and previous work), suggest the older zircon populations are related to sedimentary recycling in the Gondwanide Orogeny. The youngest and dominant population contain elongate euhedral grains interpreted to be directly derived from their protolith. Since zircons form in felsic igneous rocks, and no igneous rocks of Late Permian age occur in the Karoo Basin, these findings suggest significant input of volcanic material by ash falls. These results support sedimentological and palaeontological data for a Lopingian (Late Permian) age for the upper Beaufort Group, but contradict previous workers who retrieved Early Triassic dates from zircons in ashes for the Beaufort and Ecca Groups. Pb-loss not revealed by resolvable discordance on the concordia diagram, and metamictization of natural zircons are not factored into the conclusions of earlier workers.

Clay paste characterization and provenance determination of Middle and Late Helladic vessels from Midea

Results of the Neutron Activation Analysis (NAA) of 61 pottery samples of Middle and Late Helladic date from recent excavations in Midea are presented. Chronologically, the sampled pieces fall into two groups, the first of Middle Helladic and Late Helladic I/II, the second of LH III date, with most samples dating to LH IIIB or IIIC. The analyses suggest an Argive/North-eastern Peloponnesian provenance for the majority of the sampled pottery, since 26 of the samples are assigned to the NAA group Mycenae-Berbati (MYBE) and 15 to the NAA group Tiryns (TIR), including their subgroups. In addition to the two main groups the analyses include three other categories: “non-Argive”, unlocated, and singles. The differentiation into a small number of distinct chemical patterns is much more evident in the second chronological group of sampled pottery than in the earlier one which comprises a variety of chemical patterns in a small number of samples. Evidently, during the Mycenaean Palatial period several specialized workshops operated in the wider region of the North-eastern Peloponnese for the production of fine and coarse ware pottery in large quantities.

Microbial composition analyses by 16S rRNA sequencing: A proof of concept approach to provenance determination of archaeological ochre.

Many archaeological science studies use the concept of “provenance”, where the origins of cultural material can be determined through physical or chemical properties that relate back to the origins of the material. Recent studies using DNA profiling of bacteria have been used for the forensic determination of soils, towards determination of geographic origin. This manuscript presents a novel approach to the provenance of archaeological minerals and related materials through the use of 16S rRNA sequencing analysis of microbial DNA. Through the microbial DNA characterization from ochre and multivariate statistics, we have demonstrated the clear discrimination between four distinct Australian cultural ochre sites.

Ion Microbeam Analysis in Cultural Heritage: application to lapis lazuli and ancient coins

&lt;p class="Abstract"&gt;Ion Beam Analyses (IBA) techniques, for example PIXE (Particle Induced X-ray Emission) and IL (IonoLuminescence), are a powerful analytical tool used to investigate the composition and structure of materials in cultural heritage. These techniques could be applied both in vacuum preparing the sample as in electron microscopy and in the air in a non-invasive way allowing to analyse artworks of practically any shape and dimension without sample preparation. Moreover the use of a focused beam (microbeam) permits to reach an analysis resolution of few micrometers in vacuum and ten micrometers in air.&lt;/p&gt;In this work, instruments and methodologies are described and two examples of case study are reported: I) the mapping of elemental distribution in ancient roman coins; II) the trace elements measurement in lapis lazuli for provenance determination

Portable XRF: A Tool for the Study of Corundum Gems

AbstractOrigin of gemstones is a key aspect not only in gemological field but also in Cultural Heritage studies, for the correct evaluation of precious artifacts. The studies on gems require the application of non-invasive and non-destructive methods; among them, portable spectroscopic techniques has been demonstrated as powerful tools, providing a fingerprint of gems for origin and provenance determination. In this study, portable XRF spectroscopy has been applied to test the potential of the technique for the origin determination of corundum gems. The obtained results allowed distinguishing natural and synthetic rubies and sapphires.