NMR as a new tool for cultural heritage application: The provenance of ancient white marbles

Identifying the origin of marble used in antiquity brings back to light details of the economic, social and political organization of classical societies, and characterizing in depth the chemistry of marble is key to discovering its provenance. Beyond X‐ray diffraction, which could reveal the presence of discriminant secondary crystalline phases and the quantification of accessory minerals combined with a multivariate analysis approach, solid‐state nuclear magnetic resonance (NMR) enables one to recognize the local structure arrangement of both crystalline and amorphous materials by looking at one or more selected atoms. In present paper targets the ¹³C nuclide, and thus the major component of marble, calcium carbonate. Whatever their geological origin, marbles ¹³C‐NMR spectra present only one resonance corresponding to the carboxyl function whose intensity and line width vary from one marble to another. If the variation of the NMR signal intensity observed is the result of great T1 variations (from 220 to 5300 s) and is linked to iron content, the line width reflects defects in the calcite crystal in which calcium has been replaced by another element such as magnesium, aluminium or strontium. The specific profile of the NMR signal has been used successfully to help determine the origin of some archaeological items.     

五千年前陶质建材的测试研究

迄今为止的考古发掘表明,我国最早的陶质建材,应该是距今5500年左右的凌家滩“红陶块”。考古学家推测其原料为粘土矿物,烧成温度约800～1000℃,且其物理性能与砖质建材较为接近,应为“砖的雏形”,为此,本工作测试分析了凌家滩“红陶块”的物相组成、烧成温度、吸水率与抗压强度,同时对比分析了明砖、汉砖、现代砖的物理性能,发现“红陶块”系粘土原料在950℃以上温度烧制而成,其吸水率和抗压强度由外向内呈梯度变化,内层的抗压强度、吸水率接近于现代砖和汉砖,业已超过明砖样品,所有这些分析结果,皆支持考古学家关于凌家滩“红陶块”为砖的雏型的推测。     

The provenance and distribution of Early Bronze ceramics in the Kolyaei Plain,central Zagros,Iran

Within Iran, there is little archaeological evidence for relationships between newly arrived Early Trans-Caucasian (ETC) or Kura-Araxes settlers and earlier inhabitants and contact with neighbouring cultures, or for their apparently abrupt end. Based on the evidence, the Iranian Kura-Araxes was not a simple ‘copy' of the Caucasian Kura-Araxes package. Ceramic traditions show local peculiarities, and all are elements suggesting that the Kura-Araxes traditions went through processes of adaptation, change and re-elaboration according to local tastes and technologies. In this study, an archaeometric approach to ceramics in the Kolyaei Plain of central Zagros contributes to the discussion of contact and exchange between indigenous communities and several cultural spheres of influence on the Early Bronze Age (beginning in the fourth millennium bce ). Morphological data, as well as the mineralogical and chemical composition of ceramics, were applied to determine the major and trace elements of the pottery shards. Based on the trace element profiles, it can be suggested that all the pottery shards are in the same group and they strongly are local products. The ceramic provenance indicates the same patterns of material interactions during the ETC or Kura-Araxes in all the sites within the Kolyaei Plain.     

DARK AND SHINY: THE DISCOVERY OF CHROMITE IN BRONZE AGE FAIENCE*

The Late Bronze Age (1550–1200 bc ) in the Near East was a period of cultural development, international trade and technological innovation, notably in metallurgy and silicate technology. As a spin‐off of the new glass technology, new colorants were also applied to faience glazes presumably to increase their aesthetic value. Here, we report on the presence of chromite minerals in the glaze of a faience vessel from Deir ‘Alla, Jordan, 1200 years earlier than reported so far. Importantly, chromite was not only used as a greyish pigment, but also as a nucleating agent for spherulitic crystallization of augite in the amorphous glaze. These synthetic augite formations give a unique, sparkly appearance to the faience vessel, apparently imitating a metallic look. The making of such an intricate glaze and its contemporary significance reflect not only the high level but also the appreciation of innovation in that region at that time.     

Black Gloss Pottery: Production Sites and Technology in Northern Etruria,Part II: Gloss Technology

The present study aims to understand the reasons for the visual differences of black gloss pottery found in northern Etruria. The results obtained by conventional (scanning electron microscope, electron microprobe) and synchrotron (X‐ray diffraction, X‐ray absorption spectroscopy) techniques indicate that the thickness, porosity or chemical composition of the different types of gloss cannot be used as the principal distinguishing factor. The size of quartz or feldspar crystals may well be a critical factor responsible for the matt effect in some samples, while the range of mixtures of iron compounds indicated by XRD and XAS could be the reason for differences in colour and reflectivity. The Fe L‐edge XAS results in particular show that a correlation does exist between the oxidation state characteristics and the visual appearance. The Si, Fe and Al contents seem to further discriminate the different types of gloss that have differing visual appearances.     

Chemical analyses of the earliest pigment residues from the uttermost part of the planet (Beagle Channel region,Tierra del Fuego,Southern South America)

This paper presents the results of chemical analyses of the organic and inorganic fractions of pigment residues found in three archaeological sites located in the Beagle Channel region, Tierra del Fuego, Southern South America. Twenty-one archaeological samples have been analysed through XRD, SEM–EDX, FT-IR and GC–MS in order to characterise their inorganic colouring components and to search for the presence of organic substances used as binders. Lipids found in some samples are considered as potential binders. These organic components are compared to those found in archaeological sediment samples from the same layers where the pigments have been found, in order to search for potential taphonomic contaminations of the latter by the former. Results show that such contaminations are unlikely, hence the lipid contents are deemed of anthropic origin. The pigment sample results are also compared to data from analyses of natural sediment samples collected in several localities of the Beagle Channel in order to search for potential natural pigment sources. Results show that organic and inorganic components of these sediments are not the same than those present in the archaeological pigment samples, hence the pigment raw material sources have not been yet located. All these data provide for the first time evidence of the existence of ancient activities of pigment sourcing and paint preparation with organic binders which range from 6000 BP to 1900 BP in the southernmost region of the planet.     

宝鸡益门出土玉器分析研究

使用扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)对陕西宝鸡益门出土的玉器残块的显微结构、元素和物相组成进行了分析研究。结果表明,益门二号墓出土玉器分析样品属单斜闪石类型中的透闪石系,其透闪石含量在85%以上。出土玉器样品应归属为青玉种类,玉料较好,属中上水平的玉料。根据我国玉器文化的历史和和田玉的矿物特征,益门二号墓出土玉器分析样品类似于和田玉矿物。     

A MULTI‐ANALYTICAL APPROACH FOR THE CHARACTERIZATION OF COMMODITIES IN A CERAMIC JAR FROM ANTINOE (EGYPT)*

This paper describes a multi‐analytical chemical study performed on the original, almost totally conserved, content of a small ceramic jar from the Antinoe archaeological site (fifth to seventh centuries ad, Roman Egypt) and now belonging to the archaeological collection of the Istituto Papirologico ‘Girolamo Vitelli’ (Florence, Italy). Scanning electron microscopy with an energy‐dispersive X‐ray spectrometer (SEM–EDX), Fourier transformed infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) were all used to characterize the inorganic components of the archaeological material. The organic substances were analysed using FTIR, direct exposure mass spectrometry (DE–MS) and gas chromatography – mass spectrometry (GC–MS). The inorganic component essentially consisted of halite (NaCl). Among the NaCl crystals, lamellar elements were identified. They were chemically characterized by carbonato‐apatite and showed a concentric morphology typical of the scales of small fish. The most prevalent organic constituents of the sample were monocarboxylic acids, α,ω‐dicarboxylic acids, and cholesterol and its oxidation products. The organic material composition was consistent with the occurrence of lipids of animal origin. In addition, diterpenes related to pine pitch were also identified. The overall results suggest that the material recovered in the small ceramic jar found in Antinoe is a residue of fish‐based pickles such as garum, muria, allex and liquamen, which were commonly used in Roman times.     

RELATIONSHIP BETWEEN THE COLORATION AND THE FIRING TECHNOLOGY USED TO PRODUCE SUSA GLAZED CERAMICS OF THE END OF THE NEOLITHIC PERIOD*

Ancient decorated potteries from Susa (Mesopotamia) dating from 4200 to 3700 bc , were studied in order to determine the origin and the nature of the raw materials used, and to identify the technological processes applied to make the ceramic bodies and their decorations. Bulk compositions were determined by particle induced X‐ray emission (PIXE), while the microstructure and the mineralogical phases were studied using scanning electron microscopy (SEM), energy dispersive X‐ray analyses (EDX) and X‐ray powder diffraction (XRD). The results showed that the raw materials used to elaborate these potteries were similar for all the ceramic bodies (carbonates and iron and magnesium‐rich clays containing sand), and for all the decorations (iron oxides, silica, potassic and alumina sources). The variations of coloration of the ceramics and of their decorations were due to different firing temperatures. The ranges of firing temperatures used by potters were evaluated on the basis of mineral stability domains.     

The painting of the Etruscan “Tomba della Quadriga Infernale” (4th century BC), in Sarteano (Siena, Italy): technical features

This work presents the results of an investigation of the painting technique used in the Etruscan tomb “Tomba della Quadriga Infernale”. This tomb was discovered in Sarteano (Siena, Italy) in October 2003 and dated back to the second half of the 4th century BC. Red, dark red, pink, yellow, white, black, and grey colours were used in the tomb in order to create paintings, which now represent a very precious record of the Etruscan art of wall painting in a hypogeal environment. The technical features of the painting were revealed by stratigraphy using optical and electronic microscopy. The components and preparatory layers of the painted areas were characterized using Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray microanalysis (SEM-EDS), X-ray diffraction (XRD), and gas chromatography/mass spectrometry (GC/MS). XRD, SEM-EDS, and optical microscopic techniques were also used for mineralogical analysis of the rock substrate. The SEM-EDS and FTIR analyses showed that red and yellow ochre, calcite, and vegetable charcoal were used to paint the walls of the tomb: the pigments, either alone or mixed together, were utilized to produce pure colours (red, yellow, white, and black) and intermediate tonalities (pink, dark red, and grey). SEM-EDS, FTIR, and XRD highlighted that the painting was made on a preparatory layer of calcite, applied onto a levelling material made up of calcite, clay minerals, quartz, and iron oxides. GC/MS analyses revealed that egg was used as an organic binder to disperse the pigments.