指纹元素分析对南宋郊坛官窑的起源研究

选取30个南宋官瓷样品、2个效坛官窑的原料、紫金土和4个现代仿官瓷样品进行中子活化分析（NAA）,测定每个样品中36种微量元素的含量。从这36种元素中挑选出9种指纹元素的含量进行散布分析。结果表明：南宋官窑的釉料和胎料产地明显不同;南宋官窑有着长期稳定的釉料和胎料产地;遗址缸内的原料（35#）、练泥池内的原料（36#）、紫金土（37#）既不同于古官瓷的釉料,也不同于胎料。练泥地内的原料（36#）比较接近于胎料。现代官瓷的釉料和胎料与古官瓷的明显不同,说明它们的产地不同。     

High‐boron and High‐alumina Middle Byzantine (10th–12th Century ce) Glass Bracelets: A Western Anatolian Glass Industry

The trace element boron is present in most ancient glasses as an impurity, and high boron (≥ 300 ppm) marks raw material sources that are geologically specific and relatively uncommon. Recent analyses of Byzantine glass with high boron contents suggest that glass‐making was not limited to the traditional regions of the Levant and Egypt, and a production origin in or near western Anatolia is proposed. Glass bracelets from ?i?n al‐Tīnāt in southern Turkey give fresh evidence for the production and circulation of high‐boron glasses that closely correlates with object typology. The patterning of findspots suggests that high‐boron glass was closely connected to the Byzantine world.     

The origins of Byzantine glass from Maroni Petrera,Cyprus

Nineteen glasses from Maroni Petrera, Cyprus, dating to the sixth–seventh centuries ad, have been analysed by energy‐dispersive X‐ray analysis in the scanning electron microscope for major and minor elements. A subset of 15 glasses was also analysed for trace elements, using inductively coupled plasma mass spectrometry. Two groups are identified. The majority is made of glass produced in the coastal region of Syria–Palestine. The smaller group is of high iron, manganese and titanium (HIMT) glass, a widespread type of uncertain origin at the present time. The glasses appear to have undergone relatively minor mixing and recycling, and the glass material is likely to have arrived in Cyprus in the form of raw glass chunks or relatively fresh vessel cullet.     

Evidence for the trade of Mesopotamian and Egyptian glass to Mycenaean Greece

The origins of raw glass used to fashion Mycenaean beads were explored using trace elements analyzed by laser ablation ICP-TOFMS. The use of this minimally destructive technique for the in-situ analysis of these beads was ideal given that the material is exceedingly rare and thus too sensitive to make use of traditional micro-sampling (e.g., by scalpel). A wide range of trace elements were measured to compare these Greek glasses to other Late Bronze Age glass coming from Egypt and Mesopotamia. Of the eleven beads analyzed, four blue glasses colored with cobalt and two blue/green glasses colored with copper have trace element compositions consistent with an Egyptian origin of manufacture. The other five of the glasses, all colored with copper, were found to conform to the composition of Mesopotamian glass. These data are the first to demonstrate direct and clear evidence for the trade of raw glass to the Mycenaean states.     

历代耀州窑釉料渊源关系的初步分析

耀州窑是我国古代名瓷窑。为了探讨历代耀州窑釉料之间的渊源关系,用中子活化分析(NAA)技术测定古耀州瓷釉样品和耀州窑博物馆附近粘土矿样品中29种元素的含量,将这批NAA数据进行模糊聚类分析,得到动态模糊聚类分析图。结果表明：唐代的黑瓷釉原料产地非常集中,矿料成分单纯。宋代青瓷釉料配方比较稳定,五代青瓷具有承前启后的作用。金代月白釉料成分和宋代青瓷釉料接近。唐三彩蓝釉料与其他耀州瓷釉料来源明显不同。     

ROMAN WINDOW GLASS: A COMPARISON OF FINDINGS FROM THREE DIFFERENT ITALIAN SITES

Thirty‐three samples of window glass and five glass lumps coming from three Italian archaeological sites—the Suasa excavations (Ancona, settled from the third century bc to the fifth to sixth centuries ad ), the Roman town of Mevaniola (Forlì‐Cesena, settled from the Imperial Age up to the fourth century ad ) and Theodoric's Villa of Galeata (Forlì‐Cesena, settled from the sixth century ad onwards)—were analysed to track the changes in the chemical composition and manufacturing technology of window glass through the centuries. The aims of this study were: (1) to establish the origin of the raw materials; (2) to verify the chemical homogeneity among samples coming from different sites and/or produced using different techniques; and (3) to sort the samples into the compositional groups of ancient glass. The analysis of all the chemical variables allowed two groups to be distinguished: (a) finds from Mevaniola and Suasa; and (b) finds from Galeata. All the samples had a silica–soda–lime composition, but the analysis of minor elements—in particular, of Fe, Mn, and Ti—made it possible to split the samples into two groups, with the higher levels of these elements always found in the Galeata samples (HIMT glass). In conclusion, it can be asserted that the main differences between the samples are related to their chronology.     

Visigothic Jewellery: A Technical Study of Glass Used as Gems in Belt Buckles from a Spanish Necropolis

In this work, we studied coloured and colourless glass used as gems in Visigothic buckles possibly originating from the necropolises of Torredonjimeno, Duraton or Castilltierra in Spain. Scanning electron microscopy (SEM) with energy‐dispersive analysis (EDS) and observations made with an optical microscope in reflected and transmission mode were performed in order to establish the composition, origin of the colour and decay process of these glass pieces. The chemical analysis of ancient glass can provide relevant information regarding the manufacturing approach used during a specific period. The results revealed the presence of various transition metal elements used as chromophore elements, as well as some metallic backing foils used to improve the colour of pieces of almost colourless glass.     

Evidence for glass ‘recycling’ using Pb and Sr isotopic ratios and Sr-mixing lines: the case of early Byzantine Sagalassos

The secondary production (working) of glass from imperial to early Byzantine times has been proven at the ancient city of Sagalassos (SW Turkey) by the existence of glass chunks, fuel ash slag and kiln fragments related to glass processing. It had been previously suggested that local green glass might have been recycled from two other locally found glass types (blue glass vessels and chunks and HIMT glass chunks). This paper provides analytical evidence for the recycling of glass next to the use of imported raw glass. The heterogeneous lead isotopic composition of the green and HIMT vessel glass at Sagalassos, with as end members on the one hand the isotopic composition of local blue glass vessels and chunks and on the other hand that of the HIMT glass chunks, could indicate the production of ‘recycled’ glass, although heterogeneous raw materials could have been used. However, the use of Sr-mixing lines confirms local recycling. It is clear that the Sr in the green and HIMT vessels is a mixture of the Sr in the aforementioned end members. It cannot be proved whether the green ‘recycled’ glass was produced from a mixture of chunks alone, or from a mixture of cullet and chunks. Suggestions are made towards the possible origin of the raw materials for the blue and HIMT glass on the basis of Sr isotopic signatures and absolute Sr contents in the glass.     

Wavelength‐dispersive X‐ray fluorescence analysis of ancient glasses*

The application of X‐ray fluorescence to the study of the composition of ancient glasses has been limited by the large amount of material required for samples. In this paper the setting of a reduced sampling XRF method for the analysis of ancient glasses is described. The method involves the preparation of glass beads by melting the sample with lithium tetraborate flux. By means of reference and synthetic samples, the method allows regression curves to be set, covering broad ranges from ppm to high concentrations. By means of a single program, up to 31 elements of interest in the study of ancient glass are analysed. The reproducibility, sensitivity and reliability of the method are discussed. The results demonstrate that 0.2 g of glass is sufficient to obtain accurate and sensitive analyses for most of the elements of interest.     

Pliny the Elder and Sr–Nd isotopes: tracing the provenance of raw materials for Roman glass production

In Roman and Byzantine times, natron glass was traded throughout the known world in the form of chunks. Production centers of such raw glass, active from the 4th to 8th century AD, were identified in Egypt and Syro-Palestine. However, early Roman primary glass units remain unknown from excavation or scientific analysis. The ancient author Pliny described in 70 AD that besides Egyptian and Levantine resources, also raw materials from Italy and the Gallic and Spanish provinces were used in glass making. In this study, the primary provenance of 1st–3rd century AD natron vessel glass is investigated. The use of combined Sr and Nd isotopic analysis allows the distinguishing and characterizing of different sand raw materials used for primary glass production. The isotope data obtained from the glass samples are compared to the signatures of primary glass from known production centers in the eastern Mediterranean and a number of sand samples from the regions described by Pliny the Elder as possible sources of primary glass. Eastern Mediterranean primary glass has a Nile dominated Mediterranean Nd signature (higher than −6.0 ? Nd), while glass with a primary production location in the western Mediterranean or north-western Europe should have a different Nd signature (lower than −7.0 ? Nd). Most Roman glass has a homogeneous ⁸⁷Sr/⁸⁶Sr signature close to the modern sea water composition, likely caused by the (intentional) use of shell as glass raw material. In this way, strontium and neodymium isotopes now prove that Pliny's writings were correct: primary glass production was not exclusive to the Levant or Egypt in early Roman days, and factories of raw glass in the Western Roman Empire will have been at play.     

Chemical and lead isotope analysis of some lead-barium glass wares from the Warring States Period,unearthed from Chu tombs in Changde City,Hunan Province,China

In the context of the present study, we have conducted chemical and lead isotope analyses on twelve ancient glass samples unearthed from Chu tombs in Changde City, Hunan Province. The results of the chemical analysis of these samples show that all samples are PbO–BaO–SiO₂ glasses, thus indicating that they are all traditional ancient Chinese glasses. The chemical results also suggest that all Bi wares may either share a common source or were produced according to similar recipes. In turn, the eye beads are different from the Bi wares for their distinct chemical composition. The chemical results indicate that silica, lead-bearing material, barium-bearing material, and sodium/lime-bearing material are the main independent components of the raw materials employed in the production of these glass wares.     

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.     

ICP-MS trace element analysis of Song dynasty porcelains from Ding,Jiexiu and Guantai kilns,north China

Bodies of Ding kiln white porcelains and their imitations from Guantai and Jiexiu kilns of the Chinese Song dynasty (960–1279 AD) were analysed for 40 trace elements by inductively coupled plasma mass spectrometry (ICP-MS). Numerous trace element compositions and ratios allow these visually similar products to be distinguished, and a Ding-style shard of uncertain origin is identified as a likely genuine Ding product. In Jiexiu kiln, Ding-style products have trace element features distinctive from blackwares of an inferior quality intended for the lower end market. Based on geochemical behaviour of these trace elements, we propose that geochemically distinctive raw materials were used for Ding-style products of a higher quality, which possibly also underwent purification by levigation prior to use. Capable of analysing over 40 elements with a typical long term precision of <2%, this high precision ICP-MS method proves to be very powerful for grouping and characterising archaeological ceramics. Combined with geochemical interpretation, it can provide insights into the raw materials and techniques used by ancient potters.     

ANALYSIS OF LATE BRONZE AGE GLASS AXES FROM NIPPUR—A NEW COBALT COLOURANT

A multidisciplinary study of a unique group of Late Bronze Age (LBA) ceremonial glass axe heads and other artefacts shows that these are the first significant group of glasses coloured with cobalt to be identified from the Near East. The axes were excavated from the site of Nippur, in present‐day Iraq. Several are incised with the names of three kings, which dates the material to the 14th–13th centuries bc . Analysis by laser ablation inductively coupled plasma mass spectrometry (LA–ICPMS) indicates that the glass had high magnesia (MgO) and potash (K₂O) associated with a plant‐ash flux and was coloured blue by copper or a combination of copper and cobalt. These glasses are similar, but not identical, in major element composition to blue‐coloured glasses manufactured in ancient Egypt and elsewhere in Mesopotamia in the same period. However, the Nippur cobalt‐ and copper‐coloured glasses exhibit significantly different trace elemental compositions compared to Egyptian glass coloured with cobalt, showing that the ancient Near Eastern glassmakers had clearly identified and utilized a distinctive cobalt ore source for the colouring of this glass. Since it was previously thought that the only cobalt ores exploited in the LBA were exclusively of Egyptian origin, this new finding provides new insights on the origins of glass and how it was traded during the Bronze Age period.     

青海大通县出土汉代玻璃的研究

本文共对12件玻璃样品进行化学组成分析.其中,部分样品还进行了密度测定,X 射线衍射分析和显微镜观察.此外,还对一颗黄色玻璃珠的表面层进行 SEM-EDX 分析.结果表明,该玻璃珠表面有金箔涂层.根据分析结果,青海大通县出土玻璃的基础成分可归为三类,即铅钡玻璃(Na_2O-PbO-BaO-SiO_2系统玻璃),钠钙玻璃和钾硅玻璃(K_2O-SiO_2系统)。此外,还对玻璃的来源进行了探讨.     

基于造纸原料分析中国手工造纸术的传承特点

对古代中国主要造纸原料发展脉络进行了梳理,并分析目前我国手工纸造纸原料现状,最后对古今中国传统手工造纸原料进行比较研究,可知当今中国传统手工纸在原料种类、比例、处理方式等方面与古代相比较,还是发生一定的变化,正是由于这样一些变化,导致手工纸质量参差不齐,很难保持其原有的特性。     

Radical changes in Islamic glass technology: evidence for conservatism and experimentation with new glass recipes from early and middle Islamic Raqqa,Syria*

The chemical analysis of excavated glass fragments from dated archaeological contexts in Raqqa, Syria, has provided a detailed picture of the chemical compositions of artefacts deriving from eighth to ninth and 11th century glassmaking and glassworking activities. Evidence for primary glass production has been found at three excavated sites, of eighth to ninth, 11th and 12th century dates; the first two are discussed here. The 2 km long industrial complex at al‐Raqqa was associated with an urban landscape consisting of two Islamic cities (al‐Raqqa and al‐Rafika) and a series of palace complexes. The glass fused and worked there was presumably for local as well as for regional consumption. Al‐Raqqa currently appears to have produced the earliest well‐dated production on record in the Middle East of an Islamic high‐magnesia glass based on an alkaline plant ash flux and quartz. An eighth to ninth century late ‘Roman’/Byzantine soda–lime recipe of natron and sand begins to be replaced in the eighth to ninth century by a plant ash – quartz Islamic soda–lime composition. By the 11th century, this process was nearly complete. The early Islamic natron glass compositional group from al‐Raqqa shows very little spread in values, indicating a repeatedly well‐controlled process with the use of chemically homogeneous raw materials. A compositionally more diffuse range of eighth to ninth century plant ash glass compositions have been identified. One is not only distinct from established groups of plant ash and natron glasses, but is believed to be the result of experimentation with new raw material combinations. Compositional analysis of primary production waste including furnace glass (raw glass adhering to furnace brick) shows that contemporary glasses of three distinct plant ash types based on various combinations of plant ash, quartz and sand were being made in al‐Raqqa during the late eighth to ninth centuries. This is a uniquely wide compositional range from an ancient glass production site, offering new insights into the complexity of Islamic glass technology at a time of change and innovation.     

ELECTRON PROBE MICROANALYSIS OF MIXED-ALKALI GLASSES

European mixed-alkali glasses are compared with Sayre and Smith's categorisation for ancient glass and with the chemical compositions of other prehistoric and later European glasses. The new categories reported here indicate that a wide range of alkali raw materials was used in the production of glasses found in prehistoric European contexts. At least five major chemical categories of glass are now known to have been used in prehistoric and early Roman Europe. A plant species of the genus Sulicorniu is suggested as a possible alkali source in ancient European glasses.     

Trace element discriminants between Egyptian and Mesopotamian Late Bronze Age glasses

The origins of Late Bronze Age glass artefacts found throughout the Mediterranean and Near and Middle East remain controversial. Previous analyses of major and minor elements in both Egyptian and Mesopotamian glasses have proven equivocal, revealing no significant compositional differences between glasses from these two regions. Here we present new Laser ablation-ICPMS analyses of 32 trace elements in 54 samples of both Egyptian and Mesopotamian blue and colourless glasses. Our results show that there are consistent differences between these two suites, which are not related to the colorant and clearly indicate the use of different raw materials and/or manufacturing processes. Compositional variations are related to geological controls, hence this method holds promise for the development of a minimally destructive technique for discriminating between archaeological glasses of different provenance, which will be essential in the interpretation of ancient trade patterns and contacts.     

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.