Micro‐Raman spectroscopic study of cord‐marked pottery decorated with red coatings from Taiwan,ca 2600–1700 B.C.

Micro‐Raman spectroscopy is applied for the first time to identify mineralogical characteristics of ceramic bodies and red coatings on decorative cord‐marked pottery (ca 2600–1700 B.C.) from an archeological site in northern Taiwan. X‐ray diffraction and scanning electron microscopy‐energy dispersive X‐ray spectrometry were used as complementary techniques. The combined results of mineralogical and elemental composition suggest that the pottery items were produced from illitic clays and fired to a temperature less than 800 °C under oxidizing conditions. The slight discrepancy in composition between the red coatings and ceramic bodies possibly indicates a somewhat different source of raw materials and/or clay refining processes used by ancient potters. Additionally, feldspar, hornblende, and pyroxenes detected in the samples are closely related to the main compositions of nearby volcanic rocks, implying that the raw materials could have come from a local source. Copyright © 2010 John Wiley & Sons, Ltd.     

Micro‐Raman and infrared analysis of medieval pottery findings from Braničevo,Serbia

A selection of Byzantine table pottery (17 samples) dating from the period between the beginning of the 12th century and the first half of the 13th century, discovered at Braničevo in Serbia, were analysed by Fourier transform infrared, micro‐Raman and scanning electron microscopy with energy dispersive spectroscopy and petrography analysis. The aim of the investigation was to determine the chemical and mineralogical composition of the body and of the glaze and thus to determine the production technology. Fourier transform infrared spectroscopy provided data for estimating the firing temperature and the basic mineralogical composition, and micro‐Raman spectroscopy was applied to study and characterise both the glaze and the body of the analysed sherds. It was found that noncalcareous clays, characterised by a rich mineral assemblage, were fired at temperatures between 700 and 900 °C. Oxidizing atmosphere was applied in the production of the red colour pottery. The dark and grey coloured paste of one group of sherds was produced by firing organic matter‐rich clays in a reducing environment. The main type of transparent glaze was identified as lead‐rich, and two samples were alkali–lime glazed. Copyright © 2011 John Wiley & Sons, Ltd.     

Quantitative non‐destructive determination of trace elements in archaeological pottery using a portable beam stability‐controlled XRF spectrometer

A portable beam stability‐controlled XRF spectrometer developed at the LNS/INFN laboratories at Catania (Italy) was used for the non‐destructive determination of some trace elements (Rb, Sr, Y, Zr and Nb) in fine pottery artefacts. The XRF system and the method developed to control the energy and intensity stability of the excitation beam are briefly discussed. Concentrations of Rb, Sr, Y, Zr and Nb were determined in 50 fine potsherds from the votive deposit of San Francesco in Catania by using a multi‐linear regression method. Additionally, in order to test the homogeneity of the material composing the fine pottery samples, a small portion of a few potsherds was powdered and analysed using the XRF system and the multilinear regression method. A comparison between non‐destructive and destructive approaches is presented and discussed. Finally, quantitative XRF data were compared with those obtained by chemical analysis of the powdered samples. The results allowed the testing of a non‐destructive methodology to be used for the identification and grouping of the different typological classes of fine pottery mainly represented in the San Francesco sanctuary. Copyright © 2005 John Wiley & Sons, Ltd.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

An integrated spectroscopic approach to investigate pigments and engobes on pre‐Roman pottery

Painted Canosa ceramics were examined to identify the nature of the pigments employed and their manufacturing technology. A multi‐technique approach was used, comprising Raman microspectroscopy and laser ablation hyphenated to inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The analysed samples were mainly produced for burial in tombs and were not intended for everyday use. They belong to the period between the end of the mid‐7th century and the first half of the 4th century BC, and were excavated from the Toppicelli archaeological district near the suburbs of Canosa (Puglia, Italy). Forty‐eight pottery fragments were available for this study. No handling of the samples was required for the Raman study, and it was possible to excise the pigmented layer in such a way that the lacunae were not distinguishable to the naked eye due to the micrometric size of the laser spot as far as LA‐ICP‐MS is concerned. Their combination turned out to be quite useful for the investigation of these archaeological materials: the chemical nature of the white, red, brown and black pigments employed in the pottery manufacture was investigated. Iron and manganese compounds were identified as the red and brown/black main colouring substances, respectively; on the other hand, whites and engobes (whitish slips) were based on kaolinite. This set of colouring substances is of importance, as it enabled the artisan to obtain in one oxidising firing cycle brown, black and red paints. Finally, the finding of manganese black in these Canosa potsherds confirms that Canosa was an important centre connecting the near East to central Italy and Europe since the pre‐Roman age. Copyright © 2010 John Wiley & Sons, Ltd.     

Technological features of ‘gnathia’ pottery

‘Gnathia’ pottery samples, dating back to the mid‐fourth and third century BC, from the archaeological site of Egnazia (Fasano, Brindisi, Italy) have been characterised from the physical‐chemical, mineralogical and morphological points of view. Optical and scanning electron microscopy, X‐ray energy‐dispersive spectroscopy and X‐ray diffraction analyses have been carried out on the ceramic body, black gloss, white, yellow and red over‐paintings of fragments, with the aim of outlining technological features and defining the nature of coatings and decorations. Analytical results confirm from both a technological and morphological/decorative point of view the close relationship between ‘Gnathia’ pottery and red figured pottery, particularly with the Apulian red figured from which it takes its inspiration. At the same time the experimental results highlight shared characteristics and differences with both Attic and Apulian red figured productions. The biggest difference is in the utilisation of the ‘ingobbio rosso’ layer that covers the ceramic body. This does not seem to be based on aesthetic grounds, as in the case of Apulian red figured pottery, but on application of acquired production processes, since ‘Gnathia’ pottery was made in the same workshops as red figured pottery. Copyright © 2009 John Wiley & Sons, Ltd.     

Applications of a synergic analytical strategy to figure out technologies in medieval glazed pottery with “negative decoration” from Italy

Glazed pottery with “negative decoration” samples, dating back to the twelfth to thirteenth century ad and coming from three sites along the Adriatic coast, Siponto, Egnatia and Trani (Southern Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Optical microscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy, X-ray diffraction and micro-Raman spectroscopy investigations were carried out on ceramic bodies, pigments and glazes of the fragments. We aimed to outline the technological features, define the nature of decorations and coatings—glazes and engobes—and look for clues to hypothesize provenance. Results obtained show clear differences in raw materials and production technology between the impressed ceramic of Islamic tradition and the incised one of Byzantine tradition. Regarding the latter, evidences of a non-local origin can be found in the compositional diversity of raw materials used for the ceramic bodies of fragments decorated with spiral and pseudo-kufic motifs, which stressed the use of clays so far not recorded in Apulia. At the same time, at least in the case of Siponto, the compositional similarity of both ceramic bodies and materials used under the glaze for impressed ceramic and painted polychrome ceramics (RMR and protomaiolica), more likely local production, could suggest that both were produced in the same workshops.     

Raman Microspectroscopic study of Iberian pottery from the La Vispesa archaeological site,Spain

Raman microspectroscopy has been employed for the characterization of 16 samples of ancient Iberian pottery. These sherds of vessels were found in the archaeological site of La Vispesa in Tamarite de Litera (Huesca, Spain) and correspond to the Iberian time. The composition of certain mineral phases such as non‐plastic inclusions has been particularly considered with a view to obtaining information on the source materials and their provenance, as well as the technological conditions of ceramic production. Typical minerals such as calcite and quartz were found in most of the samples. The presence of anatase in a group of the samples suggested the use of different clays in the production of the vessels. Furthermore, the absence of rutile in these samples, together with the identification of calcite, is indicative of a mild firing temperature. Hematite was identified in all samples, both in the ceramic body and in the decoration. Differences in the position of the bands and relative intensities characterized hematite in terms of crystallinity and origin. An attempt to assign the samples to different production centers was made according to their chemical composition and morphology. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of pottery from the Republic of Macedonia I: Raman analyses of Byzantine glazed pottery excavated from Prilep and Skopje (12th–14th century)

In order to gain some understanding of and to characterize the materials used in Byzantine glazed ceramic finds in the Republic of Macedonia, as well as to obtain information on their manufacturing technology, micro‐Raman spectra of 15 representative glazed shards, all dated from 12th to 14th century, were recorded. The elemental composition of the body and glaze of selected shards was obtained by scanning electron microscopy‐energy dispersive X‐ray spectrometry (SEM‐EDXS). At least 17 different minerals in the ceramic body were identified from the Raman spectra, among which were a variety of feldspars (microcline, albite and sanidine) as well as andradite, apatite and forsterite. According to the identified minerals, locations of the used raw materials in the vicinity of the archaeological sites are proposed. There is a good correlation between the polymerization index derived from the Raman spectra and the lead content obtained from the SEM‐EDXS analyses, therefore the firing temperature of the analyzed glazes could be assessed. The SEM‐EDXS analyses showed the presence of different coloring agents (Cu, Co, Cr, Sb) as well as opacifying (Sb) and fluxing (Pb) agents in the glaze matrix. The content of P₂O₅ in the glaze of one of the shards is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Combined XRF‐SEM analysis of varnished pottery: the case of Syracuse and Adrano (Sicily) archaelogical finds

Micro‐destructive and non‐destructive X‐Ray fluorescence techniques and scanning electron microscopy coupled with energy‐dispersive spectrometry have been applied for the analysis of ten samples of Hellenistic black‐varnished pottery, coming from archaeological excavations in Syracuse and Adrano (South Italy, Sicily). Micro‐morphological and compositional investigations, together with statistical data processing, have shown several differences among the varnishes of the specimen found in the two sites. In particular, Syracuse varnishes are characterised by a more homogeneous composition and well‐defined raw materials, whereas Adrano samples show a higher variability, probably linked to the use of different raw materials and the poorer quality of the varnish as well. The obtained results attest that, as Syracuse black pottery is concerned, the production technique is at an advanced level, whereas Adrano manufacture seems to be less specialised. Copyright © 2012 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopy of decorated pottery from the Iberian archaeological site of Puente Tablas (Jaén,Spain, 7th–4th century B.C.)

In this paper, Raman spectroscopy is used for the first time to identify the pigments on decorated antique Iberian pottery. Ceramic fragments of type Real and others from the archaeological excavation in the oppidum Puente Tablas were examined. Different types of iron oxide pigments (hematite and goethite) were identified, along with amorphous carbon. In some samples, the presence of chalk or gypsum could be demonstrated. Some unattributed Raman bands are believed to be associated either with post‐burial organic deposition or with silicate materials that are present in red ochre. It was possible to relate the findings with geological data from the region and to make assumptions on a local production. Copyright © 2009 John Wiley & Sons, Ltd.     

Difference in radiocarbon ages of carbonized material from the inner and outer surfaces of pottery from a wetland archaeological site

AMS (Accelerator Mass Spectrometry) radiocarbon dates for eight potsherds from a single piece of pottery from a wetland archaeological site indicated that charred material from the inner pottery surfaces (5052 ± 12 BP; N = 5) is about 90 (14)C years older than that from the outer surfaces (4961 ± 22 BP; N = 7). We considered three possible causes of this difference: the old wood effect, reservoir effects, and diagenesis. We concluded that differences in the radiocarbon ages between materials from the inner and outer surfaces of the same pot were caused either by the freshwater reservoir effect or by diagenesis. Moreover, we found that the radiocarbon ages of carbonized material on outer surfaces (soot) of pottery from other wetland archaeological sites were the same as the ages of material on inner surfaces (charred food) of the same pot within error, suggesting absence of freshwater reservoir effect or diagenesis.     

WDXRF和FTIR对古滇国遗址出土陶器的初步分析

利用波长色散型X射线荧光光谱（WDXRF）和傅里叶变换红外光谱（FTIR）对环抚仙湖分布的澄江学山、金莲山和江川光坟头3个古滇国遗址出土的陶器从化学、结构组成以及烧成温度3方面进行了初步分析.WDXRF主次量元素分析结果表明,各遗址同类陶器（尤其是红陶）的基本制陶原料具有相似性,黑（褐）陶中添加的助熔剂含量明显高于红陶.FTIR分析结果显示同类陶器中包含的矿物具有一致性,红陶中含有石英和疑似铁矿物,黑（褐）陶中则都添加了大量的碳酸盐矿物.基于FTIR结果还对两类陶器的烧成温度做出了初步判断,估计黑（褐）陶在600-700℃,红陶在800℃左右.黑（褐）陶中较高含量的助熔剂可能在降低烧成温度方面起到了重要作用.以上初步分析表明,3个遗址出土的同类陶器在原料选择和烧成温度方面具有相似处,遗址间可能存在密切的联系.     

Bead‐releasing agents used in the preparation of solid samples as beads for WD‐XRF measurement

This paper carries the results of an evaluation of various materials, which may be used to aid in the release of a fused bead from its mould during a wavelength‐dispersive x‐ray fluorescence (WD‐XRF) measurement. The following bead‐releasing agents were studied: NaI, LiBr, NH₄I, and LiI. Each was incorporated in different quantities, as a solid and/or in an aqueous solution, together with a flux, into samples of ceramic raw materials. Release agent interference in the WD‐XRF measurement was analysed, and the optimum quantity of release agent needed to obtain suitable beads for WD‐XRF measurement was determined. The best results were obtained for LiI, which yielded reproducible beads without significant interference in the WD‐XRF measurement when a relatively small quantity (0.11 LiI g/bead) was used. Copyright © 2008 John Wiley & Sons, Ltd.     

Archaeometry of pre‐Hispanic pottery from San Luis Potosi, México

Neutron activation analysis, Mössbauer spectroscopy and X‐ray diffraction techniques were used to characterize pre‐Hispanic potsherds and modern ceramic pottery, samples of which were collected in Tenexco, San Luis Potosi, Mexico. Elementary and spectroscopic analysis showed differences between ancient and modern ceramics. While the modern ceramics studied were practically new and not used at all, the ancient ones were probably used in domestic or ceremonial activities. Besides, the latter were kept buried for a long time, and it is quite probable that their manufacture was also slightly different from that of the former. These assumptions could provide the clues to understand some of the observed differences between the composition of ancient and modern ceramics whose raw materials may have the same origin.     

Application of multivariate statistical methods to classify archaeological pottery from Tel‐Alramad site,Syria, based on x‐ray fluorescence analysis

Radioisotope x‐ray fluorescence (XRF) analysis has been utilized to determine the elemental composition of 55 archaeological pottery samples by the determination of 17 chemical elements. Fifty‐four of them came from the Tel‐Alramad site in Katana town, near Damascus city, Syria, and one sample came from Brazil. The XRF results have been processed using two multivariate statistical methods, cluster and factor analysis, in order to determine similarities and correlation between the selected samples based on their elemental composition. The methodology successfully separates the samples where four distinct chemical groups were identified. Copyright © 2006 John Wiley & Sons, Ltd.     

An assessment study of tiles from Topkapı Palace Museum with energy‐dispersive X‐ray and Raman spectrometers

A limited number of studies concerning Ottoman ceramic technology have been performed using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. The discovery of the ceramics, which were described as ‘Iznik’, at excavation sites outside of the city of Iznik, caused disagreements over the exact origin of Iznik products. In this study, bodies, glazes, and pigments of 46 tile/ceramic shards of unknown origin, which were supplied from the vaults of Topkapı Palace Museum, and two reference tile fragments, known as Kütahya products, supplied from the demolished Surp Krikor Lusavoriç church and, additionally, two Iznik reference tiles were examined using the scanning electron microscopy‐energy dispersive X‐ray spectrometry and micro‐Raman spectroscopy techniques. Results of both techniques were evaluated together for the first time to determine the power of nondestructive Raman spectroscopy technique in differentiation of Ottoman tiles. In this work, bodies of the Kütahya tiles were found to be different than Iznik and Tekfur stone‐paste bodies, which are rich in clay rather than quartz. Two different lead‐alkali glaze compositions were found for Kütahya tiles; one was rich in PbO (over 35%) and the other one was rich in alkali (PbO less than 25%). Barite inclusions were detected in the bodies and in the glazes of some Ottoman tiles, which could be the fingerprint for the Kütahya products. It was found that the under glaze red decoration is essentially a mixture of hematite and quartz in different proportions. Shades of red decoration mainly depend on the amount of hematite in the mixture. Sixteenth century tomato red decoration contains more quartz compared with 17th century dark red decoration. This study showed that a similar technology was also applied at Kütahya in the 16th century. A linear correlation was found between the position of the Raman intense stretching peak Q₃ and lead oxide content of lead‐alkali glazes, which could allow for the differentiation of Ottoman tiles based on the nondestructive Raman analysis. This study provides an important additional reference data and discussion for the Ottoman tiles. Copyright © 2011 John Wiley & Sons, Ltd.     

A new nondestructive approach to chemical analysis of potsherds using an X‐ray fluorescence microscope: Case study about the past pottery manufacture in the Yaeyama Islands

In archeology, pottery represents an important class of artifacts giving information on the past human activity, the ecology, and ancient cultural groups. Some chemical analytic methods, including X‐ray fluorescent analysis, were adopted for the archeological study of pottery. However, these techniques also involve problems, including the destructive analysis of materials, and cannot analyze the original clay condition of pottery. To address this, we carried out nondestructive chemical analysis of 13 potsherds excavated from the Yaeyama Islands in the southern Japan archipelagos using X‐ray fluorescence microscopy. Two analytic methods were used, elemental mapping and multipoint spectral measurement, making it possible to obtain a visualized elemental distribution on potsherd surface and a detailed multipoint elemental composition of the same sample for the multivariate statistical analysis. In this study, the visualized images suggested that calcium particles were mixed to temper the materials, and their size and quantity differed between potsherds, whereas the uniformity of clay substrate, including the quantities of iron and silicon on multipoint measurement, was a characteristic of each potsherd. Therefore, principal component analysis and nonmetric multidimensional scaling analysis of the potsherds suggest that the differences between the Yaeyama Islands in terms of pottery manufacturing technology are due to chronological factors in this case. Our method represents an effective new approach to the pottery study for technological change.     

X‐ray spectrometry applied for characterization of bricks of Brazilian historical sites

This paper presents the results of X‐ray fluorescence (XRF) analysis of bricks sampled from historical places in Pernambuco, a state in the northeastern region of Brazil. In this study, twenty bricks found in historical sites were analyzed. Two bricks made in the 17th century, presumably used as ballast in ships coming from Holland, five locally manufactured bricks: one from 18th century, three from 19th century, and one from 20th century, and thirteen bricks collected from a recent Archeological investigation of Alto da Sé, in the town of Olinda. Qualitative determination of the chemical elements present in the samples was undertaken using a self‐assembled portable XRF system based on a compact X‐ray tube and a thermoelectrically cooled Si‐PIN photodiode system, both commercially available. X‐ray diffraction analysis was also carried out to assess the crystalline mineral phases present in the bricks. The results showed that quartz (SiO₂) is the major mineral content in all bricks. Although less expressive in the XRD patterns, mineral phases of illite, kaolinite, anorthite, and rutile are also identified. The trace element distribution patterns of the bricks, determined by the XRF technique, is dominated by Fe and, in decreasing order, by K, Ti, Ca, Mn, Zr, Rb, Sr, Cr, and Y with slight differences among them. Analyses of the chemical compositional features of the bricks, evaluated by principal component analysis of the XRF datasets, allowed the samples to be grouped into five clusters with similar chemical composition. These cluster groups were able to identify both age and manufacturing sites. Dutch bricks prepared with different geological clays compositions were defined.     

Direct chemical characterisation of clay suspensions by WD‐XRF

This study was performed to develop a method for directly controlling the chemical composition of clay slurries used in preparing ceramic floor and wall tile bodies by wavelength‐dispersive X‐ray fluorescence (WD‐XRF) spectrometry, without the prior need to dry and prepare the samples as fused beads or pellets for WD‐XRF measurement, owing to the importance of knowing the suspension chemical composition in real time for appropriate control of the industrial process. The study was conducted on a wide range of ceramic floor and wall tile bodies, which are used to prepare different suspensions. The influence of suspension viscosity (from 300 to 7000 cp), of suspension solids content (between 66 and 69%), and of the type of body composition (floor or wall tile) on the WD‐XRF measurement was determined. In these viscosity and solid content ranges, no appreciable differences were observed in the WD‐XRF measurement results, indicating that the possibly arising variations in viscosity and solids content in such clay suspensions in industrial practice do not influence the WD‐XRF measurement. In contrast, the type of body composition did influence the WD‐XRF measurement. The developed method is rapid, reproducible, and accurate, which was verified by analysis of the materials using the customary method of WD‐XRF measurement on fused beads. In addition, this method is cheaper and more harmless to the environment; it minimises waste generation, since no sample preparation is required and the plastic sample holders can be reused, thanks to the reusable sample holder system designed at the Instituto de Tecnología Cerámica laboratories. Copyright © 2011 John Wiley & Sons, Ltd.