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.     

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.     

MINERALOGICAL INVESTIGATIONS OF MEDIEVAL BRICK SAMPLES FROM BÉKÉS COUNTY (SE HUNGARY)

Brick samples from nine archaeological sites representing seven contemporary medieval settlements in Békés County (SE Hungary) were analysed by quantitative X‐ray powder diffraction, optical microscopic, scanning electron microscopic and coupled thermal analytical – evolved gas analytical methods. The aims of this study were to give a mineralogical–petrographical characterization of the brick samples, to gain possible information on the raw clay and the admixed materials, and to determine the firing techniques applied in medieval southeastern Hungary. The mineralogical composition of the samples suggests that the locally extracted clay was mixed with fluvial sand and wheat (Triticum monococcum L.) chaff. The moulded bricks were fired in clamps. The different degrees of calcite consumption suggest that the firing temperature ranged from ～750°C to ～950°C. Moreover, the well‐developed reaction coronas on calcite grains indicate long firing times, lasting perhaps several days.     

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.     

Materials Characteristics of Roman and Arabic Mortars and Stuccoes from the Patio De Banderas in the Real Alcazar of Seville (Spain)

This study discusses the materials and traditional knowledge used in the manufacture and application of lime mortars and stuccoes by Romans and Arabs in Seville (southern Iberian Peninsula). All of the samples studied contain calcite as a binder, combined with aggregates based on river sand from the filling materials of the Guadalquivir River's depression, located in the vicinity of the Real Alcazar Palace in Seville, Spain, where the artefacts were discovered. The Romans used high‐quality production technology, as evidenced by the careful selection of raw materials as well as by the adequate binder‐to‐aggregate ratio and the elevated homogeneity of the mortars and stuccoes. The suitable distribution of aggregates resulted in higher density values for Roman fragments than for Arabic ones. Results derived from Arabic samples suggest a decline in technology manufacture over time. This work provides useful information, particularly regarding the Roman and Arabic periods in the Iberian Peninsula. The analytical techniques employed in this study were X‐ray diffraction (XRD), X‐ray fluorescence (XRF)—using conventional and portable systems, scanning electron microscopy (SEM), petrographic microscopy, differential thermal analysis/thermogravimetry (DTA/TG), particle‐size analysis and mercury intrusion porosimetry.     

The Characterization of Vegetable Tannins and Colouring Agents in Ancient Egyptian Leather from the Collection of the Metropolitan Museum of Art

This work characterizes both tanning and colouring materials found in ancient Egyptian leather objects from the Metropolitan Museum of Art. The analytical investigations focused on assessing the development of the technology of ancient tanners using high‐performance liquid chromatography (HPLC), surface‐enhanced Raman spectroscopy (SERS), X‐ray fluorescence (XRF), Fourier transform infrared spectroscopy (FT–IR), X‐ray radiography and a scanning electron microscope connected to an energy‐dispersive X‐ray detector (SEM–EDX). Reference leather samples and archaeological leather objects were investigated to identify the animal skin species and the early use of hydrolyzable vegetable tannins for leather tanning. Different methods were used to colour th leather, including madder dying and staining with hematite, or painting with Egyptian blue and Egyptian green.     

Technology of Medieval Mortars: An Investigation into the Use of Organic Additives

This work proposes a multi‐analytical approach to determine the additives in historical mortars, the use of which is widely described in bibliographical sources, but has rarely been reported in the literature. A protocol to thoroughly analyse mortars was created (optical microscopy, X‐ray diffraction, infrared spectroscopy, thermal analyses and gas chromatography – mass spectrometry). These techniques, which had already been carried out on samples from various sites from the Roman to the modern era, determined that additives had only been used in the mortars from the internal masonry at our sampling site: the medieval military shipyard of Amalfi (Italy). The investigations yielded information on the production technology, and FT–IR and GC–MS revealed a saccharide material‐based additive in the mortars, of plant origin. The FT–IR spectra suggested the presence of a natural gum, which has been used since ancient times to strengthen the cohesion properties of mortars and their resistance to tensile stress.     

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.     

STUDY ON THE PROVENANCE OF XICUN QINGBAI WARES FROM THE NORTHERN SONG DYNASTY OF CHINA

The Xicun kiln in Guangdong Province was a famous porcelain kiln in the Song Dynasty of China, and for years there has been controversy over the provenance of Xixun Qingbai wares. This paper analyses Qingbai samples from the Xicun, Hutian (Jingdezhen) and Chaozhou (Guangdong Province) kilns by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and energy‐dispersive X‐ray fluorescence probe (EDXRF). The analytical results indicate that wares with a thin body excavated from the Xicun kiln site were produced in the Hutian kiln, and wares with a thick body were locally fired in Xicun; the contents of trace elements (V, Rb, Ba, Ta, Pb and Th) and the Nb/Ta ratio can be used to discriminate the products from the Xicun and Chaozhou kilns.     

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.     

Identification of Pigments in Hellenistic and Roman Funeral Figurines

Microsamples removed from funeral figurines, which were found in two Hellenistic (third to second centuries bc ) and two Roman (first to second centuries ac ) tombs in the centre of Thessaloniki, Greece, are investigated following a multi‐analytical approach. Polarized light microscopy (PLM), X‐ray fluorescence (XRF) spectroscopy, micro‐Raman spectroscopy and high‐performance liquid chromatography coupled with a diode array detector (HPLC–DAD) are employed to identify both inorganic and organic pigments. PLM is useful to reveal the combinations of the colourants, which are identified as follows. Red ochre, cinnabar, yellow ochre, Egyptian blue, carbon black, calcite, dolomite and quartz are identified using XRF and Raman spectroscopy. HPLC–DAD is used to identify the organic colourants, which are rarely detected in painted objects of the Hellenistic and Roman period. In particular, cochineal and madder are found in six samples extracted from Hellenistic figurines. This is the first study describing the unequivocal identification of cochineal in Hellenistic objects. Furthermore, madder is identified in one sample dated to the Roman period. Madder lakes detected in the samples contain high amounts of purpurin; alizarin is either not detected or detected in trace amounts.     

ANALYTICAL CHARACTERIZATION OF ROMAN PLASTERS OF THE ‘DOMUS FARINI’ IN MODENA*

The paper refers to the analytical characterization of Roman painted plasters dating back to the second century ad . The following techniques were used: optical microscopy (OM), scanning electron microscopy (SEM–EDS), micro‐Raman and Fourier transform infrared spectroscopies (µ‐Raman and FT–IR), X‐ray diffraction (XRPD), colorimetry and thermal analyses (TG/DTA). The investigation analysed the chemical composition and structure of the plasters, the chemical composition of the pigment layers, the use of binders and any chemical alteration of pigments as well as deterioration of the samples. Stratigraphic analysis of plasters allowed identification of their individual components, which proved helpful in finding out more about the mural painting technique employed.     

SCIENTIFIC INVESTIGATION OF FAIENCE FRAGMENTS ATTRIBUTED TO THE TOWN MOSAIC AT KNOSSOS*

We analysed a faience fragment from Bristol Museum and Art Gallery, to determine whether it belonged to the Town Mosaic, excavated at Knossos. Three Town Mosaic fragments from the Ashmolean Museum, Oxford were also examined. The objects were analysed using non‐destructive variable‐pressure scanning electron microscopy with energy‐dispersive X‐ray spectrometry. The Bristol object's composition and microstructures are similar to those of the Town Mosaic samples. Our results are also comparable to those from polished samples of Minoan faience (Tite et al. 2009 ), showing that VP SEM–EDX gives reliable results without invasive sampling. Silicaceous, copper‐rich microspheres were identified for the first time in two of the Ashmolean objects.     

Multi-analytical techniques for the study of pre-Columbian mummies and related funerary materials

Due to a paucity of original written information, we base our knowledge of the pre-Columbian civilizations of Latin America on archaeological and archaeometric analysis. Particularly, the analytical study of funerary materials collected by conquerors in historical times and archaeologists nowadays during their travels and expeditions contributes to a better understanding of religious practices and social organisation. In the present study, a multi-analytical approach is presented which was used for the characterisation of red and blue organic dyes, inorganic pigments and embalming materials in various archaeological finds from the necropolis of Ancòn (Peru). These included the funerary clothes belonging to a set of three mummies, dated between the 11th and the 13th century AD. Chromatographic and spectrometric techniques were used: high performance liquid chromatography with UV-Visible detector (HPLC-UV-Vis) for identifying organic dyes, scanning electron microscopy with energy dispersive X-ray spectrometer (SEM-EDX) for recognising pigments, and gas chromatography with mass spectrometric detection (GC/MS) for analysing organic embalming materials. This multi-analytical approach enabled us to characterise a range of materials. The presence of red anthraquinoid dyes and blue indigoid ones was assessed, although it was not always possible to identify the original source with certainty. Cinnabar was identified as the colouring material applied to one mummy's hair. The molecular markers of conifer resin were detected in the bandages. The analytical results highlighted the use of a number of hitherto unknown dyes and embalming materials in Peruvian funerary rituals.     

The Structure and Chemical Composition of Wall Paintings From Islamic and Christian Times in the Seville Alcazar

Wall paintings from the Islamic epoch (10th to 12th centuries) and the Christian monarchy (14th to 16th centuries) have been recovered in discarded materials and on walls after reconstruction works in the Seville Alcazar. These paintings have spent centuries underground or under a plaster coat. Portable X‐ray fluorescence (XRF) and combined XRF/X‐ray diffraction (XRD) were employed in situ, as well as scanning electron microscopy (SEM–EDX), grazing angle incidence XRD and micro‐Raman spectroscopy, on cross‐section samples to fully characterize the materials in the wall paintings. Using these methods, the fresco technique was demonstrated, and many kinds of pigments were identified in accordance with the various periods of the history of the Alcazar, thus assessing the authenticity of all the wall paintings studied here.     

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 Faragola Ceramic Collection: Ceramic Production,Consumption and Exchange in Seventh‐Century Apulia

A collection of 30 ceramic samples, 16 of coarse wares and 14 of fine painted wares, have been investigated by optical microscopy, scanning electron microscopy, inductively coupled plasma optical emission spectrometry, inductively coupled plasma mass spectrometry and neutron activation analysis. Further samples of clayey sediments, both locally outcropping and found within the settling tank, have been submitted to the same analytical techniques for comparison with the ceramic collection. The results demonstrated that local clayey sediments were used as received for the production of coarse wares. The same raw materials were sieved and/or refined by decantation for the production of fine painted wares, which, in fact, provided results that were perfectly comparable with those for the clayey raw materials found within the settling tank. The Faragola productions were distinguished from the neighbouring Apulian productions according to petrographic features (the presence of leucite‐bearing volcanic rocks and Mn‐rich wads) and their bulk chemical composition.