Archaeometric analysis of ceramic production in Tiwanaku state (c.500–1000 ce): An exploratory study

The chemical and mineralogical characterization of seven ceramic fragments produced within Tiwanaku state (c.500–1000 ce ) is reported. The instrumental techniques used included X‐ray elemental and mineralogical chemical analysis, Raman spectroscopy, and scanning and light microscopy. The results indicate there are several clay types, although they show similarities, such as the use of a plant‐based temper. The red colour of the decoration is hematite, and manganese oxides such as jacobsite are present in the black. The white colour is a mixture of gypsum and clay, and the orange is a mixture of hematite and clay. The use of colours, the quality of the clays and the temperatures reached during pottery firing point to expertise in ceramic production and to complex decision‐making processes. The multi‐elemental archaeometric approach documented here could become an important tool to shed a light on ancient ceramic technology and the internal variance of Tiwanaku pottery.     

Investigation of Organic Materials From the ‘Royal’ Burials of Xiongnu (Noin‐Ula,Mongolia) by Srxrf and XAFS Methods

The burials of famous Xiongnu people are a unique source of information about Xiongnu culture, due to the variety of organic findings. SRXRF analysis of hair, clay, bones, teeth and woollen cloth was carried out. An anomalously high copper content was observed in all hair samples, whereas the levels of copper in bone and clay were low. To define the hair morphology and the elemental distribution in the hair cross‐section, high‐resolution X‐ray computed tomography (HRXCT) and energy‐dispersive spectroscopy (EDS) with scanning electron microscopy (SEM) were used. The X‐ray absorption fine‐structure method (XAFS) was applied to determine the local copper environment. The majority of the copper species in the hair and enamel samples are present as Cu²⁺ cations in a distorted octahedral (4 + 2) coordination, surrounded by light ligands (oxygen/nitrogen). A similar distorted octahedral coordination is typical for both inorganic mixed oxide/hydroxide Cu nanosystems and metal–organic Cu complexes (with oxygen/nitrogen).     

Physico‐Chemical Characterization of Pigments and Binders of Murals in a Church in Ethiopia

Here, we report the physico‐chemical characterization of wall paintings from the Petros and Paulos church in Ethiopia. This work represents the first technical study of paintings located in Ethiopia, rather than paintings in museum collections outside the country, using diverse analytical techniques. In situ examination with a portable X‐ray fluorescence spectrometer (pXRF) was followed by analysis of samples using optical microscopy (OM), scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM/EDS), micro‐Raman spectroscopy (MRS), attenuated total reflection – Fourier transform infrared spectroscopy (ATR‐FT–IR), X‐ray powder diffraction (XRD) and pyrolysis gas chromatography – mass spectrometry (Py‐GC/MS). The paint stratigraphy, the compositions of the support material, the preparatory and painting layers were studied, as well as the morphology of the pigment particles. The results revealed the use of earth pigments and carbon black. The preparatory layer was uncommon; composed of dolomite, clay rich in clinochlore and sand, in contrast to the more common gypsum and calcite. The binder and the stratigraphic analyses suggested a distempera technique.     

PRODUCTION TECHNOLOGY OF ROMAN LEAD‐GLAZED POTTERY AND ITS CONTINUANCE INTO LATE ANTIQUITY

A broad selection of Roman lead‐glazed pottery dating from the first century ad through the fifth century ad was studied to establish locations of workshops and to address their technology of production. The ceramic bodies were analysed by ICP–AES. In addition, lead isotope analysis was undertaken on a selection of glazes. These findings suggested that there were several regions responsible for the production of lead‐glazed ceramics in the western Roman world, including central Gaul, Italy and, probably, Serbia and Romania. Using the body compositions as a starting point, the glazing techniques employed by each of the potential workshops were examined using electron probe microanalysis. It was determined that there were two primary methods of glazing. The first method used lead oxide by itself applied to non‐calcareous clay bodies, and the second method used a lead oxide‐plus‐quartz mixture applied to calcareous clay bodies. Based on these data for clay composition and glazing method, transfer of technology from the Hellenistic east to the western Roman world was proposed. Likewise, the inheritance of lead‐glazing technology into late antiquity was established by making comparisons to lead‐glazed ceramics dating to the seventh to ninth centuries from Italy, the Byzantine world and Tang Dynasty China.     

THE TECHNOLOGY OF ‘GLAZED’ RESERVED SLIP WARE—A FINE CERAMIC OF THE HARAPPAN PERIOD*

‘Glazed’ Reserved Slip Ware (RSW) is a high‐quality glossy bichrome pottery of the Indus Valley civilization, and dates to the mature Harappan period (c. 2600–1900 bc ). Scanning electron microscopy with energy‐dispersive X‐ray analysis indicates that the surface coat on RSW is composed of a pale grey vitrified clay slip, which overlies a black slip with significantly higher iron oxide. Hence the term ‘sintered’ Reserved Slip Ware is to be preferred. X‐ray diffraction analysis indicates that both the pale and black slips contain hercynite, mullite and quartz, but observation by scanning electron microscopy shows that the black slips contain higher amounts of coarser‐grained hercynite. The elemental data suggest that different clays were used to make the bodies and the slips. However, key element ratios are very close in associated black and pale slips. The grey slip may have been produced by elutriation of the fine, iron oxide‐rich clay that was used to prepare the black slip. The pale grey slip was laid over the black and removed by combing to produce a bichrome effect, which evoked semi‐precious materials such as agate. RSW was a specialist product that required significantly higher input skill and resources than the majority of Harappan clay‐based ceramics. It is a further example of the range of sophisticated Harappan ceramic wares, which included faience, fired steatite and stoneware.     

Micro‐Raman And Micro‐Stratigraphic Analysis Of The Painting Materials In The Rock‐Hewn Church Of The Forty Martyrs In Şahinefendi,Cappadocia (Turkey)

This paper presents the results of analyses carried out on the paintings on the rock‐hewn walls of the Forty Martyrs church at ?ahinefendi in Cappadocia (a UNESCO World Heritage Site), a central region of Turkey, performed during conservation work from 2007 to 2012. The micro‐samples were investigated by spectroscopic, micro‐stratigraphic and scanning electron microscopy analysis in order to study the painting technique, the materials and the degradation products. The micro‐stratigraphic analysis showed a white, sometimes pinkish, plaster. Micro‐Raman analysis, performed on cross‐sections of the mortars, enabled the detection of calcite, gypsum, anhydrite and calcium oxalate. Scanning electron microscopy and energy‐dispersive spectroscopy revealed a similar composition among all investigated phases, aside from minor differences such as the presence of diatoms in the second and third phases and of biotite, lime lumps and plants fragments in the fourth one. Apart from traditional pigments of medieval wall paintings, micro‐Raman analysis revealed the presence of lead‐based compounds and jarosite.     

Can the Raman spectrum of anatase in artwork and archaeology be used for dating purposes? Identification by Raman microscopy of anatase in decorative coatings on Neolithic (Yangshao) pottery from Henan,China

Scanning electron microscopy/energy dispersive X-ray analysis has earlier shown that the white background layer (slip) on painted pottery sherds (Yangshao culture, Henan, China, 4200 BC) is composed of kaolinitic clay containing titanium in the assumed form of TiO₂ at just 1 wt%. The same samples of white slip have now been studied by Raman microscopy, revealing bands characteristic of anatase, but none from the majority species, the matrix of kaolinitic clay. These results highlight the extraordinarily intense Raman scattering from even trace amounts of anatase and thus the need to recognise that, although the colours of archaeological artefacts are almost always determined by the nature of the matrix, the Raman spectrum may be determined by a highly scattering trace component such as anatase. The significance of anatase as a potential date-marker pigment on works of art and archaeological artefacts is discussed.     

Petrology and Geochemistry of Late Intermediate Period Ceramics,Southern Peru

Multiple petrological and geochemical analytical techniques revealed significant similarities in element and mineral distribution between the 47 ceramic samples from Chillo (southern coast, Peru), a Late Intermediate Period (ad 1000–1400) archaeological site. The similarity indicates a common raw material source. The analytical results of Holocene fluvial sediment samples, Cretaceous clay layers and fired and non‐fired bricks, only eliminated the Cretaceous clay layers as a potential source material. Applying Raman spectroscopy, the red and violet colour of the slip is due to hematite, the yellow colour to a mixture of hematite, graphite and gypsum, and the black colour is either graphite or jacobsite.     

Provenance of Red‐Figure Pottery of the Classical Period Excavated at Olympia

Neutron activation analysis (NAA) has been applied to a set of red‐figure pottery fragments excavated in Olympia, in Elis: (a) to determine the provenance of these vases, since this is difficult by archaeological means, and the vessels might be local Elean or Attic, Corinthian or Italian products; and (b) to determine the characteristic elemental pattern of the clay paste prepared by the potters of this Elean region. Included for comparison are several Corinthian sherds excavated in Kyme, Italy, that are archaeologically classified as exports from Corinthia to Italy, and fragments of local Italian Corinthian imitations. The majority of the red‐figure vases were made locally in the north‐western Peloponnese and show the elemental pattern termed OlyA, which is represented in many vases and clay samples from this region that were known previously. It is not very different from the well‐known pattern of the north‐eastern Peloponnese (Argolid/Corinth) termed MYBE (Mycenae/Berbati), but can be separated by its lower Cs, Rb and K concentrations, as proven by many sherds from the Argolid and wasters from Berbati. Only a few red‐figure vessels are imports from Attica, but none come from Italy.     

PAUL‐LOUIS CYFFLÉ'S (1724–1806) TERRE DE LORRAINE: A TECHNOLOGICAL STUDY

Fragments of four Terre de Lorraine biscuit figurines were subjected to porosity analysis, X‐ray fluorescence analysis, X‐ray diffraction analysis, backscattered‐electron image analysis—coupled with energy dispersive spectrometry—and electron backscatter diffraction analysis to determine the porosity, bulk, major, minor and trace element compositions, and the composition and the proportion of their constituent phases. Cyfflé's Terre de Lorraine wares embrace two distinct types of paste, a calcareous and an aluminous–siliceous one. Both are porous (9–25% water adsorption). The former consists of a mixture of different proportions of ground quartz or calcined flint, ground Pb‐bearing glass and calcium carbonate with a refractory clay. The firing temperature was between 950 and 1050°C. For the latter, Cyfflé mixed ground pure amorphous SiO₂, ground quartz or calcined flint, ground porcelain, ground Na–Ca‐glass and coarse‐grained kaolinite with a fine‐grained kaolinitic clay. The figurines were fired below 1000°C. The result was a porous, hard paste porcelain‐like material. Cyfflé's recipes for both pastes can be calculated from the chemical and the modal analyses.     

珂罗版印刷与传统书写墨迹的比较研究

珂罗版印刷是书画文物主要复制方法之一。由于该方法复制书画真迹印刷品仿真程度高,满足了广大书画爱好者研究和收藏的需要,同时给书画真伪识别带来一定的难度。本工作通过视频显微镜、扫描电子显微镜、红外光谱、拉曼光谱等多种检测手段对珂罗版印刷油墨和传统书写墨迹进行研究。结果表明,珂罗版印刷油墨与传统油烟墨和墨汁在形貌、成分方面均存在一定的差异,从而对可疑书画印刷品的鉴别提供了科学依据。     

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.     

Lipid Residues from Low‐Fired Pottery

This paper assesses the fate of lipids associated with low‐temperature and pit‐fired pottery to determine to what degree organic compounds persist or are removed during short‐firing episodes below 800 °C. Three different types of clay were fired using contrasting techniques including at 400 °C for 4 h in a muffle furnace, and pit‐firing in which pottery was fired to higher temperatures but for shorter periods of time. Total lipid extracts obtained by solvent extraction of test sherds were screened using gas chromatography‐flame ionization detection (GC‐FID) to determine the lipid concentrations and gas chromatography–mass spectrometry (GC–MS) to identify the organic compounds present. The results showed that firing of clay removes all naturally occurring alkyl lipids; however, during pit‐firing, diterpenoid lipids were introduced into the clay as a condensate from pine ( Pinus spp.) wood used as fuel. These results confirm that alkyl lipids, e.g., fatty acids, can be reliably associated with the use of vessels, although caution is required when interpreting the origins of lipids that might derive from fuel used in firing.     

Archaeometric Investigation of Medieval Pottery from Excavations at Novo Brdo,Serbia

Medieval pottery from excavations at Novo Brdo, Serbia, an important mining and trading centre during the 14th and 15th centuries, was investigated by a combination of optical microscopy, inductively coupled plasma – optical emission spectrometry, Fourier transform infrared, micro‐Raman and energy‐dispersive X‐ray fluorescence spectroscopy and X‐ray powder diffraction methods in order to determine its composition and firing temperature. The samples investigated were made of medium‐ to coarse‐grained, non‐calcareous clay, by a relatively well‐controlled firing procedure in an oxidizing atmosphere. The firing temperature was estimated to be 850–950°C. The similarity between the chemical composition of the investigated pottery and the local raw clay, combined with the outward appearance and the archaeological findings, indicate domestic production. The pottery is covered with the transparent lead‐rich glaze. Iron and copper were used as colourants.     

Chemical and Petrographic Analysis of Pre‐Hispanic Pottery from the Southern Abaucán Valley,Catamarca, Argentina

Neutron activation (NAA) and petrographic analyses were carried out on Late and Inca Period pottery from 15 archaeological sites and several clay samples in the southern Abaucán Valley, Catamarca, Argentina. The results from the NAA and petrographic analyses provide new data concerning local versus non‐local pottery production and vessel exchange for these two pre‐Hispanic cultural periods. The chemical data demonstrate the use of different clay sources over time until the Inca appearance in the region, when a more structured and controlled production is observed. Petrographic analyses show a similar change in the ceramic paste recipes used by ancient potters.     

A SPECTROSCOPIC INVESTIGATION OF PIGMENT AND CERAMIC SAMPLES FROM COPÁN,HONDURAS*

A combination of micro‐Raman spectroscopy, micro‐infrared spectroscopy and SEM–EDX was employed to characterize decorative pigments on Classic Maya ceramics from Copán, Honduras. Variation in red paint mixtures was correlated with changing ceramic types and improvements in process and firing techniques. We have confirmed the use of specular hematite on Coner ceramics by the difference in intensities of Raman bands. Different compositions of brown paint were correlated with imported and local wares. The carbon‐iron composition of the ceramic type, Surlo Brown, was confirmed. By combining micro‐Raman analysis with micro‐ATR infrared and SEM–EDX, we have achieved a more comprehensive characterization of the paint mixtures. These spectroscopic techniques can be used non‐destructively on raw samples as a rapid confirmation of ceramic type.     

CHARACTERIZATION OF LATE CHALCOLITHIC MICRO‐BEADS FROM ÇAMLIBEL TARLASI,NORTH‐CENTRAL ANATOLIA

Micro‐bead manufacture is geographically widespread from the fifth millennium bc . Previous studies of comparable micro‐beads from sites in the Indus Valley region and the Near East suggest that many of these beads were formed from synthetic enstatite. Characterization of micro‐beads from the Late Chalcolithic site of Çaml?bel Tarlas? was carried out by optical microscopy (OM), scanning electron microscopy (SEM) and microanalysis with energy‐dispersive X‐ray spectroscopy (EDS), and X‐ray diffraction analysis (XRD). The chemical composition of the micro‐beads analysed indicated that they were made from three distinctive materials; namely, bulk talc (i.e., synthetic enstatite precursor), apatite and mineral‐rich clay pastes.     

Determining the Firing Temperature of Low‐Fired Ancient Pottery: An Example from the Donghulin Site,Beijing, China

The traditional thermal expansion method using a dilatometer fails to accurately determine the original firing temperatures of low‐fired ancient pottery. For this reason, we have developed an improved method of determining firing temperatures for low‐fired pottery. This paper explains the theory of the improved method and presents the reasonably satisfactory results obtained on ancient pottery from the Donghulin site (c. 10 000 bp ). The method and the results are very important for the study of ancient pottery culture and clay moulds used for bronze casting.     

The Potential of EBSD and EDS for Ceramics Investigations—Case Studies on Sherds of Pre‐Columbian Pottery

The work focuses on the potential of structural and chemical examinations by scanning electron microscopy based methods for archaeometric studies on ceramics. Achieved by a single preparation technique (polished block sections), the feasibility and benefits of electron backscatter diffraction are demonstrated as case studies using polychrome examples of pre‐Columbian pottery (Wari, Moche and Cajamarca). Elemental and phase maps allow for separate consideration of clay and temper. Identification of mineral phases and intergrowths of temper particles provide information for clarifying clay procurement and firing techniques with respect to local versus non‐local pottery to enlighten trade relations, technological transfer and shared heritage of pre‐Columbian cultures.