Provenance identification of ancient pottery from Hachijojima Island,part of Izu Islands (Tokyo,Japan), using X-ray fluorescence spectrometry

A total of 47 pottery fragments were unearthed in Hachijojima Island, part of the Izu Islands (Tokyo, Japan). Among these samples, 36 found in the Kurawa site had designs resembling pottery dating back to the Jomon period (14,000–300 BC) distributed throughout Japan's main island, Honshu; five samples from the Jomon period found in the Yubama site were “undesigned”; the rest, found in the Yaene site, were undesigned Haji pottery samples dating back to the beginning of the late Kofun period (490–549 AD). X-ray fluorescence spectrometry (XRF) was used to determine the chemical composition (in terms of 10 major oxides and 12 minor elements) of the samples to identify their provenance, that is, local versus nonlocal. For this purpose, a portion of each pottery fragment was processed to obtain a glass bead specimen. The pottery samples were classified by multivariate statistical approaches, including principal component analysis and cluster analysis, on the basis of their chemical composition. Additionally, the XRF results were compared to geochemical data from Hachijojima Island using scatter diagrams. The data thus collected allowed the provenance of the pottery samples to be inferred. In particular, the 36 samples from the Kurawa site were concluded to have been brought to Hachijojima Island from Honshu in prehistoric times, whereas the other samples were concluded to have been manufactured locally.     

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.     

Application of X-ray fluorescence spectroscopy to provenance studies of Algerian archaeological pottery

The North African regions boast a multimillenary tradition of pottery production that represents a decisive progress in all societies. In this paper, we present the analysis of several fragments of pottery dating from the Middle Ages and collected in the archaeological site of Gouraya in Béjaïa (Algeria). Energy-dispersive X-ray fluorescence measurements were performed to obtain the elemental composition of the clays and to attempt a classification of the samples through multivariate analysis methods, connecting them to the archaeological information about the sites. Hierarchical clusters analysis (HCA) identified two possible different groups, related to different production sites, even if only one source of clay seem to be used, consistently with the geological contest. Based on the results, a tentative provenance interpretation could be proposed on historical bases. We put in place a strategy that made it possible to perform provenance studies respecting sample integrity as we aim to extend our research also to integer and well-preserved object from museum, to create a database for Algerian production of in the Middle Ages.     

Provenance determination of prehistorical pottery from Oshima Island belonging to Izu islands (Tokyo,Japan) using X-ray fluorescence spectrometry

A total of 41 pottery shards originating in the Jomon period (14000–300 BC) and Yayoi period (300 BC–250 AD) were excavated from the Shimotakabora site on Oshima Island of the Izu islands (Tokyo, Japan). X-ray fluorescence spectrometry was used to determine the chemical composition (10 major oxides and 12 minor elements) of the potteries to identify the potteries' provenance, that is, local or nonlocal product. The calibration curves were drawn by synthetic standards prepared from a mixture of chemical reagents containing analytes, which presented good accuracy and reproducibility by analysis of the geochemical references. The pottery samples were classified by multivariate statistics such as principal component analysis and cluster analysis based on their chemical composition. Additionally, the X-ray fluorescence results were compared with geochemical data from Oshima Island using scatter diagrams. The pottery provenance was identified by their classification. This provenance estimation indicates that 37 of the 41 potteries were brought to Oshima island from Japan's main island, Honshu, in the prehistoric age.     

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.     

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.     

Chemical fate of iron in a peatland developing in the southern Espinhaço chain,Brazil

A peatland (geographical coordinates of the sampling site, 18° 05′ 43.6″ S, 43° 47′ 6.4″ W; altitude 1,330 m asl) in São João da Chapada, municipality of Diamantina, state of Minas Gerais, was sampled at different depths of two profiles with different vegetation coverings (namely, field grassland and bush) in order to collect materials that might reflect changes of the chemical states of iron over the peat formation coming from original minerals like basic rock very likely influenced by hematitic phyllite surrounding the boggy pedon. Mössbauer spectroscopy spectra at room temperature and chemical composition analysis reveal that the iron contents for the peatlands under both vegetations decreases on going from the surface downwards. Also, a central doublet of (super)paramagnetic ferric chemical species, even for samples from deeper positions on the profile, where the reducing chemical potential of the pedoenvironment is thought to be higher, dominates the spectral patterns for all samples. In agreement with the Mössbauer results, magnetic measurements give evidence that the magnetic response of the surface samples is the highest, displaying a sharp decrease below 15 cm and a slight but steady increase with depth down along the profile.     

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.     

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.     

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.     

广义模糊K调和均值聚类的近红外光谱生菜储藏时间鉴别

生菜的储藏时间是影响生菜新鲜程度的重要因素。为了快速、无损和有效地鉴别生菜的储藏时间,以欧式距离的p次方代替模糊K调和均值聚类(FKHM)中欧式距离的平方提出了一种广义模糊K调和均值聚类(GFKHM)算法并将该算法应用于鉴别生菜的储藏时间。以60个新鲜生菜样本为研究对象,采用Antaris Ⅱ近红外光谱分析仪每隔12 h检测生菜的近红外漫反射光谱,共检测三次,光谱扫描的波数范围为10 000~4 000 cm-1。首先用主成分分析(PCA)对1 557维的生菜近红外光谱进行降维处理以减少冗余信息,取前20个主成分,经过PCA处理后得到20维的数据。然后用线性判别分析(LDA)提取光谱数据的鉴别信息以提高聚类的准确率,取鉴别向量数为2,则LDA将20维的数据转换为2维数据。最后以模糊C-均值聚类(FCM)的类中心作为FKHM和GFKHM的初始聚类中心,分别运行FKHM和GFKHM计算模糊隶属度以实现生菜储藏时间的鉴别。结果表明,GFKHM的鉴别准确率能达到92.5%,FKHM的鉴别准确率为90.0%,GFKHM具有比FKHM更高的鉴别准确率。GFKHM的聚类中心比FKHM更逼近真实类中心。GFKHM的收敛速度明显快于FKHM。采用近红外光谱技术同时结合GFKHM,PCA和LDA为快速和无损地鉴别生菜储藏时间提供了一种新的方法。     

Characterization of pottery from Republic of Macedonia II. Raman and infrared analyses of glazed pottery finds from Skopsko Kale

Byzantine and Ottoman pottery shards from Skopsko Kale, Republic of Macedonia (27 samples) were analyzed by infrared (IR) and micro‐Raman spectroscopies. IR spectroscopy provided data for assessing the firing temperature of the ceramic body as well as the basic mineralogical composition, while micro‐Raman spectroscopy was used for studying the glazes as well as for estimating the mineralogical composition of the ceramic body. The firing temperature of the Byzantine pottery was more uniform and ranged between 700 and 800 °C. In the case of the Ottoman pottery, a clear distinction between two different firing temperatures in the samples was made, thereby dividing them into two groups (700–800 and 800–900 °C). According to the previously established relationship between glaze composition and Raman parameters, the glazes in all analyzed samples were found to be lead‐based, with firing temperature below 700 °C. A total of 25 different mineral phases was identified in the body of the ceramics. Some pigments were also identified in the pottery glazes. Oleic acid (oil) and apatite residues (protein?) were identified in one sample. Copyright © 2009 John Wiley & Sons, Ltd.     

基于X射线谱学和操作链分析的煤山遗址出土陶器综合研究

采用能量色散X射线荧光光谱(ED-XRF)技术结合考古学常用的陶器操作链研究模式,对河南汝州煤山遗址出土的陶器遗存开展制作工艺和文化传承关系的综合研究。煤山遗址位于河南省汝州市(原为临汝县)北刘庄村,是研究中原地区新石器时代向文明国家转变的代表性遗址,出土了龙山时代的王湾三期文化(BC2300—BC1900)和具备早期国家形态的二里头文化(BC1750—BC1500)两个重要阶段大量具有典型考古学文化特点的陶器遗存,可以据此较为深入理解距今4000年前后社会复杂化进程和国家起源等重大问题。因此,对该遗址出土陶器的多学科综合研究具有极高的学术价值和文化意义。对煤山遗址出土具有不同文化类型的陶器样本进行化学组成与物理性能分析,将分析结果与陶器操作链分析相结合,进行比对分析。针对煤山遗址陶器遗存,谱学分析结果显示,不同时期考古学文化在制陶原料的选择上差异不大,具有同源性,暗示虽然文化类型不同,但其对粘土的认识和选择具有高度一致性。陶器操作链分析结果显示,虽然新石器时代的王湾三期文化年代较早,但其陶器制作工艺却较晚期的二里头文化更先进,体现了中原地区文化演进过程中既连续又摇摆的发展特点。陶器操...     

Application of various spectroscopic techniques to characterize the archaeological pottery excavated from Manaveli,Puducherry, India

This paper is focused on a spectroscopic study of some ancient pottery shreds from an archaeological site Manaveli village, Puducherry, India. Analytical characterization using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and differential scanning colorimetric coupled with thermo gravimetric analysis were carried out on red and black ware and red ware recently excavated from the above site. The experimental results of FT-IR and XRD are similar and allowed us to identify the mineralogical composition of pottery samples. In addition, TGA was applied in order to study the dehydration of hydroscopic water and decomposition of carboxyl group in the powdered pottery samples during heating. Moreover, this paper proves that all the above spectroscopic techniques are very useful analytical tool for the examination of ancient pottery, which is also suitable for the identification of its firing temperature and firing atmosphere.     

Early Pottery Making in Northern Coastal Peru. Part III: Mössbauer Study of Sicán Pottery

Sicán blackware from a 1000-year old elite tomb at Huaca Loro was characterised by neutron activation analysis, optical thin-section microscopy, X-ray diffraction and Mössbauer spectroscopy. A number of blackware fragments from the later site of Puerto Pobre (ca. AD 1460–1550) were included in the analysis for comparison and found to be of different origin. The black surface of the specimens from Huaca Loro is mostly due to carbon deposition during firing in a reducing environment. Part of the pottery was merely dried at temperatures below 400°C, perhaps because it was made in haste for funeral use.     

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.     

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.     

Iron speciation in ancient Attic pottery pigments: a non‐destructive SR‐XAS investigation

The present work reports a detailed investigation on the speciation of iron in the pigments of decorated pottery fragments of cultural heritage relevance. The fragments come from the Gioiosa Guardia archaeological site in the area of the `Strait of Messina' (Sicily, Southern Italy), and date back to VI–V century BC. The purpose of this study is to characterize the main pigmenting agents responsible for the dark‐red coloration of the specimens using non‐destructive analytical techniques such as synchrotron radiation X‐ray absorption spectroscopy (SR‐XAS), a well established technique for cultural heritage and environmental subjects. Absorption spectra were collected at the Fe K‐edge on the Italian beamline for absorption and diffraction (BM8‐GILDA) at the European Synchrotron Radiation Facility in Grenoble (France). In order to determine the speciation of Fe in the samples, principal component analysis and least‐squares fitting procedures were applied to the near‐edge part of the absorption spectra (XANES). Details on the local structure around the Fe sites were obtained by analyzing the extended part of the spectra (EXAFS). Furthermore, an accurate determination of the average Fe oxidation state was carried out through analysis of the pre‐edge peaks of the absorption spectra. Samples resulted composed of an admixture of Fe₂O₃ (hematite or maghemite) and magnetite (Fe₃O₄), occurring in different relative abundance in the dark‐ and light‐colored areas of the specimens. The results obtained are complementary to information previously obtained by means of instrumental neutron activation analysis, Fourier transform infrared absorbance and time‐of‐flight neutron diffraction.     

Real‐space analysis of radiation‐induced specific changes with independent component analysis

A method of analysis is presented that allows for the separation of specific radiation‐induced changes into distinct components in real space. The method relies on independent component analysis (ICA) and can be effectively applied to electron density maps and other types of maps, provided that they can be represented as sets of numbers on a grid. Here, for glucose isomerase crystals, ICA was used in a proof‐of‐concept analysis to separate temperature‐dependent and temperature‐independent components of specific radiation‐induced changes for data sets acquired from multiple crystals across multiple temperatures. ICA identified two components, with the temperature‐independent component being responsible for the majority of specific radiation‐induced changes at temperatures below 130 K. The patterns of specific temperature‐independent radiation‐induced changes suggest a contribution from the tunnelling of electron holes as a possible explanation. In the second case, where a group of 22 data sets was collected on a single thaumatin crystal, ICA was used in another type of analysis to separate specific radiation‐induced effects happening on different exposure‐level scales. Here, ICA identified two components of specific radiation‐induced changes that likely result from radiation‐induced chemical reactions progressing with different rates at different locations in the structure. In addition, ICA unexpectedly identified the radiation‐damage state corresponding to reduced disulfide bridges rather than the zero‐dose extrapolated state as the highest contrast structure. The application of ICA to the analysis of specific radiation‐induced changes in real space and the data pre‐processing for ICA that relies on singular value decomposition, which was used previously in data space to validate a two‐component physical model of X‐ray radiation‐induced changes, are discussed in detail. This work lays a foundation for a better understanding of protein‐specific radiation chemistries and provides a framework for analysing effects of specific radiation damage in crystallographic and cryo‐EM experiments.     

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.