Archaeometric Investigations Research Articles

An EPR study of the marbles from quarries of the Denizli region (Turkey): A contribution to the provenance assessment of materials with close relationships

The analytical and spectroscopic discrimination of marbles coming from quarries used in historical times is a task object of a wide interest in archaeometric investigations. This task is even more difficult, when the goal of the provenance assessment is focused on marbles coming from historical quarries located in a close geographic area. In this paper, we present the results of a systematic Electron Paramagnetic Resonance spectroscopy study aimed at assessing the discrimination criteria among 5 quarries located in the Denizli region (Anatolia, Turkey) that were benefited in Hellenistic and Roman period to provide materials for the buildings in the nearby city of Hierapolis of Phrygia (Turkey). The resulting EPR characterisation is used, in combination with the results of isotope geochemistry and petrological observation, to define criteria able to discriminate the provenance of marble samples from the considered quarries. The criteria arose from the analysis operated through robust compositional statistical techniques over the results of the experimental investigation. In this approach, the internal structure of the multimethodic dataset was unravelled. The results here presented provide evidence of a good discriminating ability of the proposed approach.

Archaeometric Investigations on Archaeological Findings from Palazzo Corsini Alla Lungara (Rome)

This study reports the analytical investigations on clayey and ceramic finds, characterised by high variability in terms of prime materials, with the aim to determine the role of this important ceramic production situated close to the city walls, fortuitously found during service excavations developed in the garden of Palazzo Corsini in Rome. The complexity of the finds led to the choices of appropriate methodologies and techniques suitable for defining the diagnostic elements of each find. Optical microscopy (OM) combined with micro-Raman (µ-Raman) spectroscopy, X-ray diffractometry (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDS), and differential thermal analysis (DTA) were used to analyse the nature and microstructure of the ceramic and burned clay that were found. In such a complicated setting, the objective of conducting chemical analyses is to provide clues to describe the various kinds of ceramics produced, the production and processing methods, and, as a result, the typology of the workshop.

Archaeometric investigations of the Late Roman Period red slip ware from Caesarea Germanicia (Kahramanmaraş, Southeastern Anatolia)

AbstractIn the present study, red slip wares excavated from the ancient city of Germanicia (modern Kahramanmaraş, Southeastern Anatolia) were subjected to an archaeometric analysis. A multi‐analytical approach was employed, including stereomicroscopy, optical microscopy, XRPD, SEM‐EDS, and XRF to explore the mineralogical and chemical compositions of the samples. Based on both archaeological and archaeometric criteria, the samples were classified into three main categories: African, Phocaean, and Sagalassos red slip wares. The African red slip wares were characterized by an abundance of coarse quartz inclusion, accompanied by lesser quantities of plagioclase and mica. The Phocaean red slip wares primarily consisted of quartz, feldspar, and mica. In contrast, the Sagalassos red slip wares featured a groundmass rich in quartz, mica/biotite, hematite, and opaque minerals. Thermoanalytical data indicated that all samples were fired at temperatures between 800 and 900°C. The results suggest that red slip wares found at Germanicia were not manufactured using local available clay sources but rather originated from different regions. This evidence further provides that Germanicia was actively involved in trade networks and interacted with various ancient urban centers, such as Africa, Phocaean, and Sagalassos, during the Late Roman Period, between the fourth and fifth centuries AD.

Non-invasive analysis of reference glass and historical mosaic tesserae by means of reflectance infrared spectroscopy

Within vibrational spectroscopy techniques, Raman is much more employed than infrared spectroscopy for the study of glassy materials belonging to cultural heritage. This could be due to both a less straightforward interpretation of the spectra and a more difficult application of the technique with portable instrumentations. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) can be exploited in archaeometric investigations because portable and non-invasive. On the other hand, no systematic applications of this technique to historical glasses are found in the literature. This exploratory work reports the DRIFTS investigation of the Corning Archaeological Reference Glasses, widely used as references in the cultural heritage field, and of real case glass samples, with the aim of exploring the potential of this technique to gain information about their composition and alteration. The results, exploiting the association of portable X-ray Fluorescence (pXRF), and, where possible, of EDS microanalyses, are encouraging, setting the samples within a compositional range and highlighting spectral differences for the altered surfaces.

Prehistoric gold from Lake Sevan Basin? New research on Armenian gold deposits and objects

The article gives an overview of the results of a joint Armenian-German project in the area of today's open pit gold mine of Sotk in Eastern Armenia. Special attention is given to the preliminary results of the gold analysis. Interdisciplinary studies on regional natural gold deposits - especially the Sotk and Tsarasar deposits - and their archaeological context are presented together with the analytical results of 43 gold and four silver objects from five different sites in Armenia. The LA-ICP-MS data are discussed in terms of their alloy and trace element composition. They provide information on the use of raw material sources, intentional alloying, and the preferred use of these alloys. The archaeometric investigations show that the gold objects were mostly made of secondary placer gold. However, for one object, the oldest object examined in this study, the use of primary rock gold could not be excluded. Furthermore, the data provide information on the serial production of typologically identical types found at different sites, indicating that these objects were probably traded over long distances.

X‐Ray Techniques Dedicated to Materials Characterization in Cultural Heritage

AbstractThis article discusses the basic principles, methodological features, instrumental characteristics, and practical applications of X‐ray techniques in cultural heritage. X‐ray techniques are a set of well‐defined methods for determining the chemical composition and properties of samples. In the field of cultural heritage, material characterization provides valuable information on archaeological materials for understanding heritage assets and ensuring their sustainability. X‐ray fluorescence (XRF) is a versatile method for qualitative and semi‐quantitative elemental analysis. X‐ray diffraction (XRD) is a characterization method to define the properties of the crystal structure of materials. X‐ray photoelectron spectroscopy (XPS) is a chemical tool for understanding the surface chemistry of materials. X‐ray absorption fine structure (XAFS) is a powerful probe for determining the local atomic environment of individual atomic species. X‐ray imaging methods are used for visualization and examination of the objects under study, including X‐ray radiography (XRR) for the non‐destructive inspection of objects, X‐ray computed tomography (XCT) for revealing the internal structure of materials, and dual‐energy X‐ray absorptiometry (DEXA) for the diagnosis of bone health. X‐ray techniques represent key analytical techniques in archaeometric investigations and provide valuable insights into the cultural significance of artifacts.

Reflections into Ptolemaic Glass II: Characterizing Yellow, Yellowish‐orange, Red, and Brown Inlays from Tebtynis

AbstractA systematic and extensive analytical study was carried out on the loose inlays discovered in the Ptolemaic workshop of Tebtynis (Fayum oasis, Egypt). This paper presents data derived from the multi‐methodological archaeometric investigations (optical microscopy, scanning electron microscopy–energy‐dispersive spectroscopy, electron probe microanalysis, micro‐Raman spectroscopy) performed on a set of intentionally colored and opacified glasses. In particular, we will discuss the textural, chemical, and mineralogical results related to the study of the yellow, yellowish‐orange, red, and brown inlays and semi‐finished/waste products now preserved at the Museo Egizio, Torino. The results highlight the presence of natron (low‐magnesium glasses, LMG) and plant ash (high‐magnesium glasses, HMG) base glass, coexisting with intermediate composition. Yellow samples are opacified using lead antimonates doped with iron and sometimes tin; conversely, yellowish‐orange specimens and the only brown sample are characterized by nanocrystals of cuprite. Red glasses are found in two variants: Dull reds are HMG with colloidal metallic copper particles, while sealing‐wax reds show LMG composition, associated with dendritic cuprite dispersed in a transparent, greenish matrix.

CHEMICAL AND MINERALOGICAL ANALYSES OF THE LATE NEOLITHIC CERAMICS FROM ŞAH VALLEY (SINGUBER), TURKEY

Numerous settlements have been identified during the surveys in Şırnak province (Turkey) since the beginning of the 19th century. The potsherds found in the central of such settlements have been thought to be affected by Mesopotamian culture, and the ones from the hillside of the Şah Valley were considered as the most eastern examples of the Hassuna Samara culture. This study presents the results regarding one of the first detailed archaeometric investigations carried out for the Late Neolithic ceramic findings unearthed from Şah Valley (Şırnak province, Turkey). The ceramics were initially characterized by means of portable X-ray florescence (p-XRF) and X-ray diffraction (XRD) in order to enlighten the chemical and mineralogical features of the samples, respectively. The results indicated use of calcareous raw material sources and a low firing temperature range (ca. 700-800oC). The potsherds were also investigated through petrography which showed the presence of quartz, opaque minerals, plagioclase and biotite as the minerals, and clay, claystone and marl rock contents as the rock types for the samples, in general. Fourier transformed infrared (FTIR) spectroscopy was additionally applied for the potsherds. This complementary technique provided information about the vibrations of the chemical bands in the ceramics which displayed the characteristic bond vibrations of decisive minerals in the ceramic fabrics, such as calcite, clay minerals and quartz. Considering the whole archaeometric data, it can be deduced that the Neolithic ceramics of the Şah Valley have been subjected to low firing temperatures which could be assigned to a basic production procedure presumably claiming daily-use wares.

Archaeometric Investigations of the Chalcolithic Pottery from Topolița—Neamț County, Romania

The current work deals with specific investigations on the ceramic fragment samples from the archaeological site of Topolița (Eastern Romania), which is essentially unexplored to date. X-ray diffraction (XRD) has shown that the ceramics contain quartz, berlinite, mica (muscovite), calcite, and opaque minerals, such as hematite. All evidence indicates the use of raw materials with a low limestone content (poor Ca clays) for the manufacture of these ceramics (Ca < 3.6%). The wavelength dispersive X-ray fluorescence (WDXRF) measurements indicated the presence of Al, Si, Fe, Ca, Zn, P, and K. All these data are well correlated with energy dispersive spectroscopy (EDS), which is used as an additional technique of scanning electron microscopy (SEM). Through thermogravimetry and porosimetry, some information have been obtained, with the results being correlated with the chromatic parameters that characterize the samples after burning: Various shades of color (red color with sparkles and partially or totally black interior), differently colored engobes, white pigment encrusted with white color from calcite, gypsum, clays, and quartz, as well as carbon deposits in the pores of the pottery, all specific to the Chalcolithic ceramics from this region. The recorded FTIR spectra of these samples led to the identification of calcite, quartz, gypsum, and aluminum phosphate, present as berlinite in all the pottery specific to this area. In addition, the presence/absence and the amount of specific chemical elements in the white pigments (e.g., calcium, aluminum, phosphorus, silicon, sulfur) could be used as indicative for the identified mineral compounds (XRD and FTIR). Calcite and silica-rich sediments as the primary decoration pigments, have been identified in this case.

A non-destructive analytical study of cultural heritage object from Late Antiquity: gold framework and gemstone inlays

Recently found historical jewellery (Czech Republic) was subjected to detailed analyses to determine the gem inlays and the gold framework in which they are embedded. Such find fits into European jewellery archaeological artefacts containing similar stones from around the fifth century CE. The gemstones were analysed with optical microscopy and Raman micro-spectroscopy to determine their mineralogical characteristics and to find out typical structural-chemical differences based on which their provenance can be found. The results of this measurement discovered two main types of minerals from the garnet group, almandine and pyrope, where pyropes have been identified as Bohemian garnets thanks to the typical photoluminescence (PL) of chromium and vanadium impurities. The craftsmanship and processing of the goldsmith work were studied using X-ray computed tomography. Such a technique is an excellent contribution for detecting and visualising the internal parts hidden behind the placement of the stones. For this reason, 3D visualisation was used to describe and better understand all preserved parts. According to this object's very high cultural and historical value, the chosen methods are suitable for non-destructive study while proving to be essential to deepen our knowledge in archaeometric investigations focused on jewellery from Late Antiquity (with possible application to the jewellery from other periods). Based on the findings presented in this study, it is one of the world's oldest documented items using Bohemian garnets in jewellery. These findings underscore the tremendous economic and political importance of Bohemian garnet mineral resources altogether, with a second completely different type of garnet believed to have originated in distant India or Sri Lanka that was used in jewellery across Europe in Late Antiquity.

Archaeometric investigations on marble provenance of two statues from the newly uncovered Roman bath at the center of the historical Amman, Jordan

This research investigates the quarry origin of the white marble used to sculpt two draped female statues found in the newly uncovered Roman bath at the center of the ancient city of Rabbath-Ammon (Philadelphia, Amman). It aims to shed more light on the trade and origin of the marble used for sculpture at the city during its prosperous period (2nd −3rd c. AD). The use of macroscopic examination and multiple analytical techniques (X-ray diffractometry, optical microscopy, C13 and O18 isotope mass spectrometry) showed that both statues were carved out of the dolomitic Thasian-3 marble quarries at Cape Vathy, Thasos Island, Greece. The stylistic features of the two statues that were common during the late 2nd and early 3rd c. AD and the wide use and distribution of this marble in Jordan during the 2nd and 3rd c. AD might be an indication to date them to the same period of the Roman times. The assigned date concords with the time of expansion, large construction activity and prosperity of the city and the use of imported and luxury stones to carve statues and embellish the structures of the city.

A Multi-Method Study of a Chalcolithic Kiln in the Bora Plain (Iraqi Kurdistan): The Evidence From Excavation, Micromorphological and Pyrotechnological Analyses

Abstract Pyrotechnology has always been a core topic in the archaeological debate concerning phases of deep cultural transformations, such as the Chalcolithic period in the Near East (c. 6000–3500 BC). However, previous studies on pyrotechnological installations, such as pottery kilns, pertaining to this period, have often been mainly descriptive, with a limited use of archaeometric investigations. This work presents a multi-method investigation of a Chalcolithic kiln recently discovered in the Bora Plain (part of the larger Peshdar Plain, in Iraqi Kurdistan), which combines stratigraphic analysis, pyrotechnological, micromorphological, and micro-remains analyses. Since this kiln represents the first Chalcolithic architectural feature excavated in the Bora Plain, this work offers precious insights into the pyrotechnology of the period, which is still relatively poorly understood, through the reconstruction of the kiln’s use and abandonment processes. The analytical outputs can be used to compare with other Near East kilns from the Chalcolithic and later periods.

Defining Dalma: an Incipient Mountain Identity?

Abstract. The Dalma archaeological culture of the northern Zagros has intrigued archaeologists for decades with a resurgence of interest as Dalma-related sherds are found at several sites recently excavated in Iraqi Kurdistan. Research into Dalma has focused on painted and surface-manipulated vessels that are highly distinctive, especially when contrasted with the contemporary widespread black-on-buff painted ceramic traditions of Greater Mesopotamia and southern Iran. Several archaeometric investigations have established that Dalma pottery was always locally produced regardless of where it is found and shows a high degree of microscopic variation in fabrics and production methods despite the apparent uniformity of vessel shapes and decoration patterns. In order to explain this phenomenon, archaeologists have repeatedly argued that groups of pastoral nomads seasonally migrated between Dalma communities and the surrounding regions, facilitating communication within the Dalma territory and producing Dalma cooking vessels with distinct surface markings as needed. However, this model lacks supporting evidence for the existence of highly specialized, long-range nomadism during the Chalcolithic and it does not necessarily explain the centuries-long sustained marked difference between small-scale, village-based Dalma communities and the surrounding societies that were undergoing profound social transformations. Instead, I argue, the Dalma archaeological culture reflects a deliberate rejection of these new forms of social organization by communities who preferred to maintain their adaptive, egalitarian lifeways in the northern Zagros highlands.

Archaeometric investigations of the Molali pottery complex (Bronze Age, Uzbekistan): New data on technology and exchanges at the end of the Oxus Civilization

The recent excavations at the site of Molali, located in southern Uzbekistan and dated to the mid-second millennium BCE, offer new insights into the definition of the Final Bronze Age pottery complex in southern Uzbekistan and the technological and stylistic links between the potting traditions of the various cultural groups at this period. An archaeometric study has been conducted in order to characterize the various wares, investigate the compositional variability of the ceramic assemblage, and determine the provenance of the raw materials. The results from a combination of techniques (Wavelength Dispersive X-Ray Fluorescence, X-Ray Diffraction, and thin section Optical Microscopy) allowed us to identify a local pottery production of wheel-made fine ware and to determine the local/regional origin of the handmade, coarse, shell-tempered ware. Exchange relationships with ‘steppe’ populations have been confirmed; they involved not only vessels (coarse rock-tempered pots) but also pottery traditions (specific ‘steppe’-like decorations on pots of regional origin). Although not numerous, they are nonetheless evidence of large-scale connections between the settlements in the Surkhan Darya valley and other peripheral cultures and areas in the mid-second millennium BCE. The diversity of fabrics (use of various raw materials and different technological processes) is also discussed regarding the choices made for intrinsic material properties required for specific functions, highlighting the strong expertise and management acquired by the potters for the production of diverse ceramic functional categories.

Archaeology of the invisible: The scent of Kha and Merit

The burial assemblage of Kha and Merit discovered in 1906 and now preserved at the Museo Egizio in Turin (Italy) constitutes the most abundant, complete, and well-preserved non-royal Egyptian burial assemblage ever found. The discoverer of the tomb and director of Museo Egizio, Ernesto Schiaparelli, limited investigations to a few non-unique items, leaving most of the assemblage untouched. His decision has enabled contemporary scholars to study such exceptional archaeological finding with non-invasive approaches that could not be foreseen at the time. Here we show that the volatile compounds emitted by organic materials contained in vessels can be analyzed and detected directly in museums by a transportable mass spectrometer (selected-ion flow-tube mass spectrometry, SIFT-MS). The interpretation of the mass spectrometric data, supported by statistical data analysis, shed new light on the chemical nature of the organic materials preserved in 50 vessels of the Museo Egizio in a completely non-destructive way.Our study proves the reliability of SIFT-MS as a fast-screening method for archaeometric investigations directly in museum, providing the unique possibility to complement, confirm and extend the archaeological research on the use and purpose of archaeological vessels and jars.

‘Put variety in White’: Multi-analytical investigation of the white pigments inlaid on Early Chalcolithic pottery from Southern Romania

The current study aims to present and discuss the results obtained by complementary archaeometric methods applied for the first time on white pigments inlaid on excised pottery of the Boian-Vidra tradition (Early Chalcolithic, c. 4900-4600 BCE). The samples came from three settlements located in Southern Romania (Sultana-Ghețărie, Vidra, and Vlădiceasca). They were selected considering that the pottery was produced in approximately contemporary sites, located relatively close to each other in the same geographical region, namely the Romanian Plain. The experimental part included the analysis of local samples of carbonate concretions and prehistoric animal bone ash as reference materials. Archaeometric investigations consisted in applying “in-air” PIXE and EDX methods for the chemical composition, XRD and FTIR for mineralogical data, SEM for microstructure observation, and EPR for the characterisation of the paramagnetic centres. Calcite, bone ash, and silica-rich sediments were identified as the primary decorating pigments. The mixtures of calcite and bone-ash observed in 13 samples were specific to the sites at Vidra and Vlădiceasca. Silica-rich sediments from distant sources were the main whitening materials in two samples from Vlădiceasca, while for the samples from Sultana-Ghețărie, calcite was the only whitening mineral. The results show with a high degree of confidence the use of both local (i.e., carbonate neo-formations and bone ash) and exotic (silica-rich sediments) raw materials to obtain the white pigment applied to Boian-Vidra pottery. Thus, the current data show the adaptability of the potters with respect to the surrounding resources and also provide new evidence for a vast trade network of raw materials and/or finished products in the Lower Danube area during the Early Chalcolithic. The deliberate mixing of two whitening materials from different sources could be a technological choice and may highlight complex symbolic behaviours.

Archaeometric Investigation of the Kunágota-Sword : A Case Study

Among the Early Medieval double-edged swords, excavated in the Carpathian Basin, there are a few which probably have Byzantine origin. The most unique piece of this small but significant group of weapons was unearthed at Kunágota, Southern Hungary. The sword, which has a special sword-guard made of bronze, has been examined by the experts of the Archaeometallurgical Research Group of the University of Miskolc with optical microscopy, SEM-EDS, ED-XRF, and microhardness tests. The primary aim was to study the microstructure of the blade and guard. There was also an important objective of the investigations to explore the possible manufacturing technology. Due to the metallographic examination, it was possible to reconstruct the manufacturing process of the Kunágota-sword. Three samples were taken from the sword for metallographic examination, two of them (K1A and K1B) were collected from the sword-guard and one (K2) from the blade. To summarise the results, it can be established that the basic material of the Kunágota-sword guard is a heterogeneous copper-alloy with high lead content. In the core area of the blade sample a very fine pearlitic structure can be seen. Towards the edge of the blade, a martensitic microstructure can be observed which probably proves a kind of heat treatment of the sword. With the aid of archaeometric investigations, our knowledge related to Byzantine swords can be deepened. Further interesting results can be gained by comparing with the characteristics of other Byzantine swords found of the Carpathian Basin.

Non-Invasive Approach to Investigate the Mineralogy and Production Technology of the Mosaic Tesserae from the Roman Domus of Villa San Pancrazio (Taormina, Italy)

The archaeological excavations at Villa San Pancrazio (Taormina, Italy) are bringing to light a vast Roman-Imperial residential quarter featuring luxurious dwellings decorated with wall paintings and mosaic floors, pointing it out as one of the most significant archaeological sites of the city. The polychrome and black and white mosaics recovered date back to the middle Imperial period, during the 2nd century AD. This work deals with the first archaeometric investigations of the materials employed for the tesserae production with the aim of elucidating the mineralogical composition and obtaining analytical evidence that can contribute to extracting information related to their production technology. For that purpose, a non-invasive methodology, based on micro energy dispersive X-ray fluorescence (μ-EDXRF) spectrometry and Raman spectroscopy, was used to characterize a wide selection of stone, ceramic and glass tesserae. Chemometric tools were exploited to manage the large set of elemental data collected on black and white lithic samples, providing essential clues for the subsequent investigations. The results evidenced the employment of natural lithotypes (calcareous sedimentary, dolomitic and volcanic) local and imported, and also artificial materials, such as ceramic made firing magnesium-rich clays, soda-lime-silica glasses made with different opacifying and coloring agents (such as calcium antimoniate, cobalt and copper).

Archaeometric Studies on the Characterization and Deteriorations of Glass Artifacts of Su Terazisi and Kral Kızı Regions in Enez (Ainos) Excavation

Archaeometric investigations were carried out to determine and correlate the chemical contents with the layers of deterioration of the 19 glass finds dating to the Roman Period uncovered from Su Terazisi and Kral Kızı Regions of Enez (Ainos) ancient city. The physical condition of glass finds was firstly examined, the layers of deterioration on the glass surface were documented with photographs, their thickness was measured with a digital thickness meter, their colors were identified by a chromameter, and images of the bubbles and deterioration products were taken under an optical microscope. When the deterioration layers of the samples belonging to the Roman Period were examined visually and with an optical microscope, the types of deterioration resulting from the chemical composition of the glass, such as iridescence, dulling, black discoloration and pitting were identified. A table was created of the existing degree of deterioration. Micro-XRF and Polarized Energy Dispersive-X-Ray Fluorescence (PED-XRF), Scanning Electron MicroscopeEnergy Dispersive Spectrometry (SEM-EDS), and Raman (Confocal) Spectroscopy methods were used to determine the element and mineralogical contents, and the deterioration layer of the glass samples. When all the archaeometric results were evaluated, it was revealed that there was a difference between the bulk glass and the deterioration layers.

Archaeometric analyses of Early Bronze Age pottery from Khashuri Natsargora (Georgia)

Ca 50 samples of Early Bronze Age (late 4th-3rd millennium BC) pottery from the South-Caucasian province of Shida Kartli (Georgia), most of them from the site of Khashuri Natsargora, were submitted to archaeometric investigations aiming to their characterisation and to the determination of raw materials (provenancing) and production technology. The main aim of the study was to identify the distinctive features of the Kura-Araxes end Early Kurgan (Martqopi and Bedeni) pottery groups. The analytical methods included powder-XRD, OM on thin section, ICP-AES and ICP-MS for major, minor and some trace elements, WDS microanalysis on single minerals. The analyses proved that in all cases local clays were employed. They were often used as found, but sometimes tempered with volcanic sands whose composition reflects the regional geology of the production area and sometimes with the addition of grog (for the Kura-Araxes) or crushed obsidian (for the Bedeni fine group). The study of rock fragments present in the temper allowed in most cases a clear differentiation between the Kura-Araxes Ware and the Bedeni wares. Most vessels were handmade but, in the case of Bedeni fine ware, they were occasionally finished with a slow wheel. Significant differences between the Kura-Araxes and Bedeni groups were also observed in surface treatment. Firing temperatures resulted mostly in the interval of 600–800 °C.