A COMPARATIVE SCIENTIFIC STUDY OF THE EARLIEST KILN SITES OF KORYǑ CELADON*

Four of the Koryǒ dynasty's earliest kiln sites are studied for the macroscopic, compositional, and microstructural characteristics of their celadon products. Recent excavation of Sǒri and surface investigation of Kangjin sites provided new materials for closer examination of the origin and early developments of celadon technology in traditional Korea. Two other sites, Wǒnhǔngni and Osari, with archaeological characteristics in common with the oldest layer of Sǒri, are also examined. Principal component analysis of body composition shows thai Sǒri and Kangjin had better control in their choice of raw materials whereas Wǒnhǔngnt and Osari had much wider scatter, showing the more experimental nature of their operation. The early Kangjin grouped out separately primarily because of their higher Al₂O₃ content, while X-ray diffraction patterns indicate they might have been fired at a higher temperature than other groups. The Korean method of two-step firing, first at a lower temperature to bake imglazed bodies and then at a higher temperature after glazing, is evident from the earliest operations in Kangjin.     

Compositional and Microstructural Study of KoryŎ Celadon and Whiteware Excavated from SŎRi Kiln in Kyŏnggi Province

An extensive study of the composition and microstructure of celadon and whiteware sherds excavated at Sori, one of the most important sites that were active during the founding stage of the stoneware and porcelain industry in Korea, was carried out. The analysed sherds were organized according to four different levels of the excavation and four different styles of haemurigup foot rim. Principal component analysis of the chemical compositions of the sherds revealed slight differences in their body and glaze compositions between the levels of excavation. Porcelain stone with high silica and low aluminium contents was generally used as the body material and wood ash as the chief flux in the glaze. Over the period of operation, the aluminium content in the bodies of the ceramics decreased and the P₂O₅ content in the glazes increased. Glazed bodies were fired in a single step, in contrast to the two‐step method used in later ceramic production. Firing conditions were adjusted to produce vitrification of the glazes, which meant that vitrification of the ceramic bodies occurred to varying extents, mostly determined by the relative contents of flux in the body and the glaze.     

THE DATING OF ANCIENT CHINESE CELADON BY INAA AND PATTERN RECOGNITION METHODS*

In 2005, sherds of a special type of ancient Longquan celadon ware were excavated at Maojiawan, in the city of Beijing, China. Although archaeologists agree that these sherds were fired in the period between the Yuan and Ming Dynasties, their specific date is unclear. In order to solve this problem, five other groups of ancient Longquan celadon sherds of known date were selected as reference samples. The elemental body composition of all the sherds was determined by Instrumental Neutron Activation Analysis (INAA). Using the same principles as in provenance research, pattern recognition methods were used to build classification functions to specify the date of the unknown sherds. After analysing the experimental data by discriminant analysis, three classification functions were built. All the unknown sherds were classified as Ming Dynasty. This prediction is well in accordance with the fact that these sherds are similar to other Longquan Ming celadon, and so they should be fired in the same dynasty. This also verified the judgement of the Beijing Institute of Cultural Relics.     

Chemical and strontium isotope analysis of Yaozhou celadon glaze

To produce useful information about the raw materials used in northern Chinese Yaozhou celadon glazes Chinese glazes (especially the source of the calcium‐bearing flux), Sr isotope analysis has been used for the first time. Yaozhou celadon is one of the most important representatives of northern Chinese greenware. The study has enhanced our understanding of the raw material sources used to make Yaozhou glazes dating from the Tang to Northern Song dynasties. It is highly likely that ‘Fuping stone’ mentioned in the historical record is not the main raw material used to make Yaozhou celadon glazes of the Tang to Northern Song dynasties. The results of ⁸⁷Sr/⁸⁶Sr analysis of the Yaozhou celadon glazes studied produce relatively consistent ⁸⁷Sr/⁸⁶Sr isotopic signatures, with a wide variation of relatively high Sr concentrations. This is firm evidence that a calcium‐bearing plant ash was the source of the calcium and of the flux in the Celedon glazes studied, and not, as some have suggested, limestone or ‘Liaojiang stone’. The study had illustrated that the present approach has great potential in providing a new way of reconstructing porcelain glaze technology.     

Non-destructive chemical characterization of ceramic sherds from Shipwreck 31CR314 and Brunswick Town, North Carolina

The purpose of this study was to chemically and texturally characterize ceramic oil jar sherds from North Carolina Shipwreck 31CR314 and to explore the utility of environmental scanning electron microscopy/X-ray energy dispersive spectrometry (SEM/EDS) for that purpose. The oil jar sherds, widely dispersed about Shipwreck 31CR314, are morphologically similar to each other, which suggests they could be from a single jar, but with so few joins this could not be concluded with certainty. Therefore, an aim of this study was to investigate whether chemical or textural characterization of the sherds might reveal unique attributes that could distinguish individual jars; results of characterization perhaps could give information on their origin and possibly site formation processes, such as whether environmental forces could have scattered sherds of a single jar during and after sinking of the ship. Previous studies have indicated this shipwreck is likely the remnants of the Queen Anne's Revenge, flagship of the pirate Blackbeard. Sherds from this shipwreck were compared with similar oil jar sherds excavated from a land site, Brunswick Town, North Carolina, to explore the use of composition and texture as hallmarks. The chemical components of the artifacts were determined by SEM/EDS. This method of analysis is valuable for archaeological research because it is rapid and non-destructive to the ceramic artifacts. Both groups of lead-glazed coarse red earthenware sherds were texturally similar except for the glazed sides of all 31CR314 sherds that exhibited small tracks of unique crescent-shaped marks. These marks may be due to manufacturing effects and immersion in seawater, and the marks may serve as hallmarks for individual jars or potentially individual manufacturers. The sherds were generally similar in composition, but the two groups exhibited distinct differences. Brunswick Town sherds consistently contained more phosphate on unglazed sides, an average 1.46 wt.% P₂O₅, and also contained trace elements not detected in the Shipwreck 31CR314 sherds. These distinct differences could be due to different manufacturing origins for Shipwreck 31CR314 and Brunswick Town ceramics but also could reflect their subjection to different environments during use and loss prior to archaeological recovery.     

汝州东沟窑金元时期青瓷与钧瓷原料和工艺特征的比较研究

金元时期在豫西中部地区多个窑址同时生产青瓷和钧瓷,发掘于2005年的汝州东沟窑遗址即是该类窑址典型代表之一。为系统了解东沟窑青瓷和钧瓷的胎釉元素组成特征和工艺特点、揭示两类瓷器各自随时代变化的规律,本项研究采用EDXRF和OM对东沟窑遗址出土且地层明确的43件金、元时期青瓷与钧瓷标本胎、釉化学组成和工艺性能进行测试分析,探讨了胎、釉的原料配比、釉层厚度和胎釉反应层厚度等工艺特征随时代和标本类型的变化规律。研究结果表明:东沟窑同时期青瓷和钧瓷胎体元素组成较接近,而两者釉的元素组成差异明显,金元钧瓷釉的SiO2/Al2O3摩尔比值都明显高于同时代青瓷的相应比值,呈现钧瓷釉典型的高硅低铝组成特征。从金代到元代,东沟窑青瓷和钧瓷釉都呈现从钙釉向钙-碱釉的转变。本项研究还观察到金元钧瓷的釉层和反应层厚度均高于同时代的青瓷;而从金过渡到元,两类瓷片的釉层和反应层厚度均趋厚。本项研究对揭示金元时期豫西中部地区青瓷和钧瓷间的传承和演化关系提供了有意义的科技数据。     

GLASS BY DESIGN? RAW MATERIALS,RECIPES AND COMPOSITIONAL DATA*

Compositional analyses of ancient and historic glasses have often been interpreted in terms of the use of specific raw materials in glass manufacture. However, the known inhomogeneity of many glass‐making raw materials and the insolubilities of some compounds make any explanation of compositional data problematic. This paper looks at three glass‐making alkalis with a view to understanding how the compositions of these raw materials are carried through to the final glass. The chemistry and variability of the raw materials are discussed, as is their contribution to the final glass composition. In addition, the choices and decisions made by glassmakers are acknowledged in the final glass compositions. This combination of factors addresses the complexity of predicting the use of specific raw materials from the finished glass composition.     

THE APPLICATION OF A PORTABLE X‐RAY FLUORESCENCE SPECTROMETER TO THE ON‐SITE ANALYSIS OF GLASS VESSEL FRAGMENTS FROM SOUTHERN THAILAND*

Ancient glass vessel fragments belonging to the seventh to ninth centuries ad , from the Ko Kho Khao, Laem Pho and Khuan Lukpad sites in southern Thailand, were studied. The glass vessel fragment samples are a collection belonging to the Department of Archaeology, the 15th Regional Office of Fine Arts of Thailand. The chemical compositions of the glasses were analysed using a modified portable energy‐dispersive X‐ray fluorescence spectrometer (OURSTEX 100FA‐II) by the introduction of a MOXTEK^® AP3.3 polymer window (5 mm²?) to the KETEK silicon drift detector for the measurement of light elements. The non‐destructive analysis was performed at the National Museum, Phuket, in Thailand. It is shown that the glass chemical compositions belong to mineral and plant‐ash based soda–lime–silicate glass. The origins of the glass artefacts are discussed in terms of raw materials and glass decoration, and compared with previously reported similar typological glasses from sites in the port city of Rāya and the Monastery of Wadi al‐Tur in Egypt.     

A Study on the Elemental Composition of Chinese Mise Type Wares from Different Periods and Kilns

A large number of porcelain shards were unearthed at the Hehuaxin and Silongkou kilns around the Shanglin Lake, Ningbo, China, some of which had clear stratification to enable the determination of the date of firing. With the purpose of studying the elemental composition in different cultural periods and between kilns, the chemical compositions of 43 typical shards from these two kilns were determined by energy‐dispersive X‐ray fluorescence (EDXRF). The results show that the mean contents of K₂O, CaO and MnO in the glaze fluctuate in different cultural periods at the Hehuaxin kiln, but not systematically. Principal component analysis (PCA) indicates that samples from the Five Dynasties and the Northern Song dynasty are similar to each other. This shows continuity in the raw materials and firing technology between the two dynasties. Comparing the mise type wares from the Hehuaxin and Silongkou kilns in the Northern Song dynasty, we found that MnO and ZrO₂ in the glaze can be used as fingerprinting elements to distinguish between samples from these two sites. In spite of this, their chemical compositions are broadly similar. Thus, perhaps, their chemical compositions can be taken as typical for those of the mise type wares produced around the Shanglin Lake.     

NEUTRON ACTIVATION ANALYSIS OF INCA AND COLONIAL CERAMICS FROM CENTRAL HIGHLAND ECUADOR

Fifty‐three ceramic samples were collected in the area of the colonial city of Riobamba, Ecuador (today Sicalpa/Cajabamba). Neutron activation analysis was used to attempt to establish elemental compositions, and from these gain information on the manufacturing locations of these samples. Colonial samples imported from Panama were separable by their high Cs contents, and can be sorted into glazed and unglazed industries based on As and Cs. High As concentrations in several sherds indicate an origin near Cuenca, in the Southern Highlands of Ecuador, for both colonial and Inca samples. Inca and colonial Quito samples from the north of the country are identifiable through high Na combined with low Sc and Cr concentrations. Locally produced Puruhá, unglazed colonial and majolica samples form a group indicative of local Riobamba elemental composition.     

Chemical analysis of white porcelains from the Ding Kiln site, Hebei Province, China

The Ding kilns were some of the most famous early kilns of medieval China, producing huge quantities of white and cream-white porcelains of outstanding technical and aesthetic quality. Since 1949 they have been excavated three times, in 1965, in 1987, and in 2009 respectively. In this latest study 69 white porcelain sherds from assured contexts and from the 2009 excavations were analyzed using laser ablation techniques (ICP-AES). The samples date from Five Dynasties, Northern Song and Jin Dynasties respectively (early 10^th to early 13^th C CE). The results show that Ding wares of different times show different characteristics that can be demonstrated through chemical composition. During the early phase of production the Ding ware bodies consisted largely of high firing kaolinitic clays with predominantly calcareous materials as fluxes. After the early Northern Song Dynasty, some calcareous material was replaced by a more potassic material. The compositions of the glazes show a parallel evolution to the bodies. However, because the glazes are very low in titania it seems unlikely that the main clay ingredients of the bodies could have been used in the glaze recipes. For much of the kiln site’s history the glazes appear to have been made mainly from the same siliceous flux-rich materials that had been blended with the main body-clays used to make the Ding ware porcelains, plus some extra calcareous material. The P₂O₅ contents of the glazes suggest that wood ash may have been one source of CaO in the glaze recipes.     

CHARACTERIZATION OF TAKATORI STONEWARE FROM CHIKUZEN PROVINCE,JAPAN*

This study reports the findings of an examination of stonewares from the Takatori kilns of seventeenth- to nineteenth-century Chikuzen Province, Kyushu, Japan. Scanning electron microscopy and inductively coupled plasma atomic emission spectroscopy were used to determine the mineralogy and chemical compositions of the ceramic bodies. The results of this broad characterization are used to comment on the relationships between these wares and the raw materials used. Despite close similarities in some cases, it is possible to distinguish the wares of many of these kilns from each other and from outwardly similar wares from contemporary kilns in adjacent provinces.     

THE ANALYSIS OF SECOND MILLENNIUM GLASS FROM EGYPT AND MESOPOTAMIA,PART 1: NEW WDS ANALYSES*

A recent analytical study by SEM–WDS was carried out on 226 glasses from the Late Bronze Age, analysing each of the glasses for a total of at least 22 elements, the largest such analytical study conducted on these glasses. The aim of the analysis was first to identify which elements were brought in with each of the raw materials and, second, to accurately characterize those raw materials. Since different glassmaking sites in Egypt and the Near East would probably use at least some local raw materials and these raw materials will vary slightly from site to site, this has potential for provenancing the glass. Analysis showed new patterns in the compositions of glass from the various sites and led to new conclusions about the supply of raw materials and personnel for the glass workshops. This forms the basis for further work by LA–ICPMS to be presented in part 2 of this paper.     

杭州万松岭老虎洞窑青瓷的胎釉成分分析

近年来在杭州凤凰山万松岭附近发现了古陶瓷窑遗址,经初步发掘考证,有专家学者认为是南宋官窑修内司窑遗址,然而也有学者对此表示异议。本文通过对万松岭出土青瓷及相关青瓷胎釉成分的分析对比,认为万松岭老虎洞官窑就是修内司官窑,同时也论述了修内司官窑以及郊坛官窑青瓷采用的浙江地区原料,而不是从河南地区引进部分原料烧制。     

PETROGRAPHIC AND GEOCHEMICAL EVIDENCE FOR LONG‐STANDING SUPPLY OF RAW MATERIALS IN NEOLITHIC POTTERY (MENDANDIA SITE,SPAIN)

Pottery from the Neolithic Mendandia site has been studied. The radiocarbon dating of the site corresponds to a range of dates from 7488–7546 cal bc to 5283–5437 cal bc : the first occurrence of pottery is dated at 5968–6040 cal bc for the lower level III, and up to 5386–5560 cal bc for level II. The antiquity of the potsherds places them within the oldest pottery production sequences in the Iberian Peninsula, which adds to the interest of this study. Ten potsherds from level II and five from level III are analysed for their petrographic and chemical characterization. The petrographic data show two different methods of raw materials manufacture—intentionally tempered pottery (ITP), using calcite and/or limestone and grog, and naturally or non‐intentionally tempered pottery (NTP). According to the matrix paste features, on the basis of the amount, shape, and average or size range of the mineral inclusions, clayed (type A) and sandy (type B) paste types were established and related to two different source areas. The chemical features also indicate two raw material sources and are in agreement with the petrographic paste types. The absence of significant chemical and mineralogical differences between the pottery from levels II and III suggests two contrasting areas for raw materials supply that lasted for at least 600 years.     

FIRING ANALYSIS OF SOUTH-EASTERN MISSOURI INDIAN POTTERY USING IRON MÖSSBAUER SPECTROSCOPY*

The Mössbauer spectra of prehistoric pottery and clay from the Malden Plain of south-eastern Missouri, USA, were examined. The pottery dates from AD 500 to 1400. The earlier sherds were tempered with sand and the later ones with shell. The sherds and clay contain a mixture of illite, smectite, and kaolinite. Most samples of clay and sherds contained both ferric and ferrous species. The spectral parameters for the ferric species were %DLE_Q～0. 7—1.1 mms^-1 and δ～0.0–0.3 mms^-1 for the ferrous species, ΔE_Q～2.1–2.7mms^-1 and δ～0.7–1.0mms^-1. The ferric to ferrous ratio is more accurately determined from the spectra than from consideration of the colour or the firing core of the sherds, which are not always related to the iron species ratio. Differences among sherds in the ferrous ΔE_Q can be related to original temperature of heating but with low precision.     

慈溪越窑和洪州窑瓷片的X荧光分析研究

用能量色散型X荧光分析仪测量了慈溪寺龙口等6个越窑窑址和洪州窑4个窑址出土瓷片胎釉的化学组成。在两地均观察到近距离窑址出土瓷胎间化学组成的差异,观察到越窑瓷釉配方的稳定性和南宋晚期时的明显进步,提出了洪州青瓷中铁含量从东汉到晚唐的马鞍形变化,可能反映洪州窑在晚唐的衰落和低铁原料的不易获得。     

A non-invasive study of Roman Age mosaic glass tesserae by means of Raman spectroscopy

Ancient mosaic tesserae are a range of materials of very varied and complex nature, including pottery, stone and glass. Raman spectroscopy is a powerful tool for the analysis of all these kinds of materials. In the particular case of glasses, this technique can be used both for a study of surface weathering and for the characterization of bulk structure, but it has not yet been extensively used for the characterization of mosaic glass tesserae. We carried out Raman analyses on a set of Roman and Late Antiquity period mosaic glass samples, which allowed a good characterization of both the glass matrix and the crystalline inclusions. All the samples show the typical Raman signatures of soda-lime-silicate glasses. Several crystalline phases were also identified, being relics of raw materials used during the glass manufacturing process, such as quartz and feldspars, or linked to the glass color/opacification, such as bindheimite and cuprite. The analyses also led to the identification in some blue, turquoise and green tesserae of calcium antimonate, whose Raman signature has only recently been recognized in the scientific literature on mosaic glasses. Some emphasis is given to the analysis of red lead-containing tesserae, colored with Cu⁺ ions or even Cu⁰ (or Au⁰) metal nanoparticles. Samples with peculiar compositions, as well as “modern” (and restoration) samples, could quite easily be distinguished from the ancient ones by their Raman spectra.     

Inheritance relationship between Zhanggongxiang kiln celadon and Ru Guan celadon: Comments on the rationality of Raman Ip value evaluating firing temperature

The development of Chinese ceramics culminated during the Song dynasty. At this time, exquisite celadon works emerged, such as Ru Guan celadon and Southern Song dynasty official kiln celadon, which exhibited the glory of their era. Since the excavation of Zhanggongxiang kiln celadon in Ruzhou city, Henan province, China, it has been attracting widespread scholarly attention at home and abroad. Most scholars have suggested that Zhanggongxiang is the official kiln of the Northern Song dynasty. In this paper, taking the celadon unearthed from the Zhanggongxiang kiln as a sample, the combination of laser Raman spectrum and thermal expansion methods is used to study the inheritance relationship between Zhanggongxiang celadon and Ru Guan celadon in the firing process. Meanwhile, the rationality of using Raman I_p value to evaluate the firing temperature of ceramics is reviewed. The main conclusions are as follows. First, the firing temperature of Zhanggongxiang celadon with various glaze colours is quite different, whereas the firing temperature of the same glaze colour is similar, thereby inheriting the firing technology of Ru Guan porcelain. Second, the I_p value of glaze cannot evaluate the firing temperature of porcelain with similar firing temperature. The I_p value corresponds to a range, within which it does not fully conform to the rule that the larger the I_p value, the higher the firing temperature. The I_p value is also associated with the formulation in addition to firing temperature. It is applicable to evaluating porcelains with a similar formulation but a large temperature difference.     

Defining the provenance of red slipped pottery from Texas and Oklahoma by petrographic methods

Ceramics are among the most important artifacts that archaeologists use to reconstruct patterns of prehistoric trade and exchange. Petrographic analysis of ceramic thin-sections, in addition to providing detailed technological data, enables the identification of sand-tempering agents. These raw materials are potentially important evidence for ceramic provenance, assuming that such common materials themselves would not have been traded. Here we apply methods developed by sedimentary petrographers to the problem of determining the provenance of Red Slipped sherds from late Prehistoric (c. AD 1000–1400) sites in the Caddoan area and contemporaneous Plains Village sites. Modal frequencies of different kinds of quartz, feldspars and lithic grains are used to construct several triangular graphs that reveal compositional patterns indicative of provenance. Sherds from the Plains Village sites exhibit higher frequencies of lithic grains, feldspars and polycrystalline quartz relative to the sherds from sites in eastern Texas and eastern Oklahoma. While anomalous sherds were identified, the longstanding assumption that Red Slipped sherds in Plains Village contexts were traded from the Caddoan area is not supported by these data. These methods have strong application potentials for other, geologically diverse portions of North America.