THE JUDICIOUS SELECTION AND PRESERVATION OF TUFF AND TRAVERTINE BUILDING STONE IN ANCIENT ROME*

The Republican and early Imperial monuments of Rome are, for the most part, built of tuffs quarried from at least seven pyroclastic deposits erupted from nearby Monti Sabatini and Alban Hills volcanoes. Remarks by Vitruvius (2.7.1–5), field observations of the monuments, and petrographic and rock testing studies of samples from Roman quarries demonstrate that Roman builders developed a good knowledge of the diverse material properties of the tuffs over centuries of use and exposure. Measurements of compressive strength, specific gravity, water absorption and adsorption of water vapour confirm that the petrographic characteristics of each tuff lithology strongly influence its strength and durability. Early construction utilized weakly durable, soft or vitric tuffs such as Tufo del Palatino or Tufo Giallo della Via Tiberina that are susceptible to decay, as at Temple C (290 bc ) of the Largo Argentina Sacred Area. Late Republican structures, such as the Temple of Portunus (80–90 bc ), employed somewhat durable, vitric–lithic Tufo Lionato reinforced with travertine, a durable limestone quarried near Tivoli. Roman builders selected the material properties of the tuffs to advantage for specific structural elements within large public monuments of the first century bc and the first century ad , as at the tabernae of the Forum of Caesar (46 bc ), where an upper storey of lightweight Tufo Lionato is supported by robust, lithic–crystal Lapis Gabinus pillars and flat arches reinforced with travertine. The tuffs are not very durable building stones; Romans preserved them with protective stucco, and travertine and marble cladding. Their high water intake, coupled with direct exposure to rain, daily fluctuations in relative humidity and urban weathering at present makes them especially vulnerable to decay.     

DISCOVERY AND CHARACTERIZATION OF AN UNKNOWN BLUE‐GREEN MAYA PIGMENT: VESZELYITE*

Blue‐green mosaic and polychrome masks and funerary offerings from the royal tombs of Calakmul, Mexico, were analysed by scanning electron microscope equipped with energy dispersive X‐ray spectroscopy (SEM‐EDS), X‐ray diffraction (XRD), and particle induced X‐ray emission (PIXE). This led to the first identification of the use of veszelyite, a rare hydrated copper‐zinc phosphate, as green pigment. Analyses of a geological sample of this mineral have been done to confirm the characterization of this Mayan pigment, which might help determine pre‐Columbian trade routes of precious and luxury objects in the ancient Maya Classic period (ad 250–800).     

MINERALOGY OF BOHEMIAN GREEN EARTH PIGMENT AND ITS MICROANALYTICAL EVIDENCE IN HISTORICAL PAINTINGS

While the most famous historical green earth deposits in Italy and Cyprus were exceptionally rich in celadonite, the deposits near Kadaň, Czech Republic, consisted of thin Fe‐rich celadonite impregnations accompanied by interstratified celadonite/smectite. In superimposed tuffs, smectites become prevalent and their colour changes from forest to olive green. Powder X‐ray microdiffraction and infrared microspectroscopy permit us to distinguish between green earth minerals in microsamples taken from works of art. The Ti contents and the Fe/Mg ratios help to indicate the presence of Bohemian green earth from Kadaň. We found this material in local 18th‐century works of art and also in paintings by Anton Kern (1709–47).     

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 CHARACTERIZATION OF PAINTS AND WATERPROOFING MATERIALS FROM THE SHIPWRECKS FOUND AT THE ARCHAEOLOGICAL SITE OF THE ETRUSCAN AND ROMAN HARBOUR OF PISA (ITALY)*

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography – mass spectrometry (GC–MS), energy‐dispersive X‐ray microanalysis (EDX) and X‐ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family. The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long‐chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships’ hulls.     

THE EFFECT OF SALTS ON THERMAL AND HYDRIC DILATATION OF POROUS BUILDING STONE*

Fifteen desalinated sandstone drill core samples from Umm Ishrin Sandstone Formation in Petra (Cambrian age) were used for this study. The samples were mineralogically analysed using X‐ray diffraction and their physical properties were also determined. Samples with similar physical properties and mineralogical composition were taken for further experimental work. After desalination, thermal and hydric dilatation coefficients were measured, then three types of salts (NaCl, KCl and Na₂SO₄·10H₂O), which have high solubility and consequently are the most dangerous to building stone (and are also detected in the sandstone monuments in Petra), were introduced into the samples and their contents were calculated. The results show that salt crystallization in the pores of building stones can increase their thermal dilatation and decrease their hydric dilatation to varying extents, depending on the nature of the salt. The average increase in the thermal dilatation coefficient per unit mass of salt is the lowest for the Na₂SO₄·10H₂O‐salted samples with a value of 5.3%, while the NaCl‐salted samples have the highest value with 7.8% per salt mass. The average percentage of the decrease of the hydric dilatation coefficient is 1061% for Na₂SO₄·10H₂O‐salted samples per mass of salt content; the NaCl‐salted samples have a value of 1510% per mass of salt content, and the KCl‐salted samples almost the same value. For the salt‐free samples, it was found that in climatic conditions with a high temperature range, the deterioration of sandstone due to temperature fluctuation is more effective than that caused by change in the moisture content, while samples with high salt content suffer more from hydric dilatation.     

RESEARCH ON THE PIGMENTS FROM PAINTED CERAMICS EXCAVATED FROM THE YANGQIAOPAN TOMBS OF THE LATE HAN DYNASTY (48 BC – AD 25)

The analysis of pigments on painted ceramics excavated from the Yangqiaopan Tombs of the late Western Han Dynasty was undertaken using optical microscopy (OM), micro‐Raman spectroscopy (μ‐RS), scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM–EDS), X‐ray diffraction (XRD) and Fourier‐transform infrared spectroscopy spectra (FTIR). The pigments were identified as red lead (Pb₃O₄), carbon (C), malachite [Cu₂CO₃(OH)₂], Chinese purple (BaCuSi₂O₆) and illite {[K,H₃O]Al₂Si₃AlO₁₀(OH)₂}. Fibrous materials were observed in some pigment samples. When observed by SEM, one showed a large amount of fibre in solidified gum, which indicated that gum of ramie could have been used as the binding medium to make the pigment particles adhere together. These results provide significant insights into the characteristics of these pigments in the Qin and Han Dynasties.     

UNIQUE PRE‐ROMANESQUE MURALS IN KOSTOĽANY POD TRÍBEČOM,SLOVAKIA: THE PAINTING TECHNIQUE AND CAUSES OF DAMAGE

Pre‐Romanesque murals at Kosto?any pod Tríbe?om, Slovakia, have been investigated by portable X‐ray fluorescence and by microanalytical methods to identify painting materials (pigments and binders), and to explain the degradation of colours. Today, missing green and blue shades have been reconstructed according to residual concentrations of Cu, which correspond to copper chlorides—products of salt corrosion of the copper carbonates azurite and/or malachite, accelerated by micro‐organisms. As confirmed by powder X‐ray microdiffraction, original minium (Pb₃O₄) has been transformed to brown–black plattnerite (PbO₂). In increased humidity, even insoluble pigments are washing down from the walls and the intensity of colours further diminishes.     

MULTIANALYTICAL STUDY OF PALAEOLITHIC REINDEER ANTLER. DISCOVERY OF ANTLER TRACES IN LASCAUX PIGMENTS BY TEM*

Palaeolithic and modern reindeer antler were analysed using complementary techniques to evaluate the conservation state of bone material. X‐ray diffraction, FT‐IR spectroscopy, scanning electron microscopy (SEM–EDX) and transmission electron microscopy (TEM–EDX) as well as proton induced X‐ray and γ‐ray emission (PIXE–PIGE) at the particle accelerator AGLAE, C2RMF were applied. This study enabled us to define the chemical and structural features of ancient antler at the micro‐ and nanometre scale and compare them to those of other bone materials such as bone and ivory. Antler is richer in its organic fraction compared to bone and ivory. Its mineral fraction, carbonated hydroxylapatite, shows very specific crystal shapes at the nanometre scale. This specific property allowed us to recognize antler traces in pigment samples originating from rock art paintings in the Lascaux cave, Dordogne, southwestern France, Magdalenian period. Therefore, TEM–EDX is the technique of choice for characterizing antler traces in complex mixtures. In the paint material of Lascaux, antler seems most likely to be a pollutant introduced either by stirring the pigments in water with a piece of antler or by carving antler artefacts next to the preparation of paint material. However, it could eventually be used as a marker of paintings that were created contemporaneously.     

The Compositional study of ceramic samples from tombs dating to the Zhou Dynasty at Xiaoshan,Zhejiang Province (China)

Xiaoshan in Zhejiang Province was an important ceramic production area in ancient China. During recent years, local archaeologists have found a number of mound tombs dating to the Zhou Dynasty and the Spring and Autumn period. Many shards of stamped stoneware and proto‐porcelain have been unearthed from these tombs. In this paper, we report how we collected ceramic shards from tombs and samples from local ancient kilns as reference materials in order to clarify their relationship. We have used the energy‐dispersive X‐ray fluorescence technique to analyse the chemical composition of the ceramic samples. The results indicate that some of the tomb artefacts may be imported from other production areas. We infer that the other tomb samples were produced at local kilns, but due to production process–related compositional differences, there are small differences in chemical composition between different categories of samples.     

First Evidence Of The Use Of Freshwater Pearls As A Cosmetic In Ancient China: Analysis Of White Makeup Powder From A Northern Song Dynasty Lv Tomb (Lantian,Shaanxi Province,China)

The Lv family tombs in Lantian, Shaanxi Province are one of the most important archaeological sites of China in recent years, providing numerous objects and a wealth of information for the study of the history of the Northern Song dynasty. There were a large number of exquisite cultural relics unearthed from the tombs, including one porcelain box containing white powder, which was identified as women's makeup. The phase composition, microstructure, thermal properties and characteristics of the trace elements in the unearthed white cosmetic powder were comprehensively analysed by X‐ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry – thermogravimetry (DSC–TG), Fourier transform infrared (FT–IR) microscopy and inductively coupled plasma atomic emission spectroscopy (ICP–AES). The white makeup powder was determined to be a product made from high‐quality freshwater pearls. These results, for the first time, showed evidence that freshwater pearl powder was used as a cosmetic in ancient China using archaeological objects, providing scientific evidence and new clues to enrich and expand research into the ancient Chinese cosmetic materials.     

A SCIENTIFIC INVESTIGATION ON THE PROVENANCE AND TECHNOLOGY OF A BLACK‐FIGURE AMPHORA ATTRIBUTED TO THE PRIAM GROUP*

The restoration of a Greek black‐figure amphora provided an opportunity to study the provenance and production technology of the vase. The composition of the ceramic body, determined by inductively coupled plasma optical emission spectroscopy (ICP–OES), matches that of Attic products. Investigation by X‐ray diffraction and reflectance spectroscopy suggests a maximum firing temperature around 900°C and a body re‐oxidation temperature around 800°C, respectively. The morphology and composition of black, red and dark red surface areas were studied by scanning electron microscopy and X‐ray energy‐dispersive analysis; the black areas show the features of a typical well‐vitrified black gloss, while the red areas were most probably obtained by simple burnishing of the body; the dark red additions, on the other hand, are the likely result of a partial re‐oxidation of a clay–ochre mixture.     

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).     

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.     

MICROSTRUCTURE OF FLINT AND OTHER CHERT RAW MATERIALS*

The crystallite size, microstrain, stacking disorder and moganite content of flint and other chert raw materials were studied by X‐ray powder diffraction profile analysis. The broadening of the X‐ray reflections of all microfibrous quartz varieties is due to both anisotropic small crystallite size and anisotropic microstrain. The microstructure varies for samples of different origin. The moganite content and the number of structural defects are higher in flint than in older chert and petrified wood. The X‐ray diffraction pattern of the cortex of flint differs from that of the core material, whereas those of the patina and the unweathered interior of the rocks do not.     

AN INVESTIGATION INTO THE RELATIONSHIP BETWEEN THE RAW MATERIALS USED IN THE PRODUCTION OF CHINESE PORCELAIN AND STONEWARE BODIES AND THE RESULTING MICROSTRUCTURES*

The microstructures of porcelain and stoneware bodies from north and south China, spanning the period from the Tang to the Ming dynasty (7th–17th centuries ad ), were examined in polished sections in a scanning electron microscope (SEM) after etching the sections with hydrofluoric acid (HF). Mullite, present as fine, mainly elongated crystals, is the dominant crystalline phase observed. The bulk chemical compositions of the bodies are determined by energy‐dispersive spectrometry in the SEM, and the relative amounts of mullite and quartz present in the different ceramics are estimated from X‐ray diffraction measurements. Mullite formed from areas of kaolinitic clay, mica particles and feldspar particles is distinguished through a combination of the arrangement of the mullite crystals, and the associated SiO₂/Al₂O₃ wt% concentration ratios. It is shown that very different microstructures are observed in ceramic bodies produced using kaolinitic clay from north China (Ding porcelain and Jun stoneware), porcelain stone from south China (qingbai and underglaze blue porcelain and Longquan stoneware), and stoneware clays from south China (Yue and Guan stonewares). Therefore, SEM examination of HF‐etched, polished sections of the bodies of high‐refractory ceramics has considerable potential for investigating the raw materials used in their production.     

FIELD AND LABORATORY MULTI‐TECHNIQUE ANALYSIS OF PIGMENTS AND ORGANIC PAINTING MEDIA FROM AN EGYPTIAN COFFIN (26TH DYNASTY)

This paper describes the physico‐chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy‐dispersive X‐ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro‐Fourier‐transform‐infrared (micro‐FTIR) and a Fourier‐transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography – mass spectrometry (GC–MS) and micro‐FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X‐ray diffraction (XRD) and scanning electron microscopy – energy‐dispersive X‐ray (SEM–EDX) in addition to the above‐cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.     

PROVENANCE OF OBSIDIAN EXCAVATED FROM LATE CHALCOLITHIC LEVELS AT THE SITES OF TELL HAMOUKAR AND TELL BRAK,SYRIA*

X‐ray fluorescence and laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) analyses conducted on 40 obsidian samples from the Late Chalcolithic 2 levels at Tell Hamoukar and Tell Brak in north‐east Syria have shown trends towards the exploitation of obsidian sources in the eastern Taurus. While the Bingöl region appears to provide the majority of obsidian to both sites, there is also evidence of more minor exploitation of a source in the Lake Van area and an altogether unknown source (X). This paper presents the data acquired from the analyses of the archaeological obsidian and situates these results within their chronological and regional contexts.     

CHARACTERIZATION OF PLASTERS FROM PTOLEMAIC BATHS: NEW EXCAVATIONS NEAR THE KARNAK TEMPLE COMPLEX,UPPER EGYPT*

The aim of the present work is to characterize plasters from Ptolemaic baths recently discovered in front of the Karnak temple complex, by the excavations of an Egyptian–French team. The characterization was carried out by means of optical microscopy (OM), scanning electron microscopy (SEM) equipped with an energy‐dispersive X‐ray detector (EDS), X‐ray diffraction analysis (XRD) and Fourier transform infrared spectroscopy (FT–IR). The results allowed the identification of the chemical composition and structure of these plasters. In addition, samples of red, yellow, black and white pigments were examined and identified. The results helped in providing an image concerning some materials used during the Ptolemaic era in ancient Egypt.     

Compositional study of bronze vessels from the Derveni tombs of central Macedonia of the fourth century bce using energy‐dispersive micro‐X‐ray fluorescence (EDμXRF) spectrometry

The chemical composition of 61 copper alloy vessels was studied non‐invasively by energy‐dispersive micro‐X‐ray fluorescence (EDμXRF) spectrometry. The vessels were found in five tombs (A, B, D, Z and H) at Derveni in central Macedonia, Greece, which belong to the cemetery of the ancient city of Lete. The tombs are dated to the last quarter of the fourth century bce . The opulence of the numerous grave offerings denotes the high social status of the deceased within Macedonian society. The material under study was divided into two main groups according to their appearance and use. The first group included 44 vessels with a golden appearance for use in banquets; the second group consisted of 17 dark vessels for domestic use. The aim of this research was to study the vessels' technology according to their chemical composition. Both golden and dark vessels consisted of a binary Cu‐Sn alloy and a slight amount of impurities (Fe, Ni, Zn, Pb, As, Co, Sb, Ag, Ti). It is probable that during construction the ancient metalsmiths were taking into account criteria such as the desired appearance, cost of metals, future use and physical properties such as resistance to corrosion. Banquet vessels had a consistent chemical composition in all their different parts compared with those for domestic use. The only chemical element used systemically for alloying purposes, except Sn, was Pb in order to improve the castability of the bases and handles of the vessels. The study provides additional information about the metalworking of bronzes in central Macedonia in the fourth century bce, as well as about the access Macedonian metalworkers had at the time to the raw materials for such use.