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。陶器操作链分析可以反映文化内容的特征性和继承性,在使用谱学分析排除了原料与烧制影响后,对其所提取的信息具有更强的说服力和可比性。综合研究表明,将谱学分析和陶器操作链分析相结合,开展多学科对比和综合研究,可以更好的排除干扰,获取更为扎实且客观的认识,并为考古学文化演进研究提供重要的科学依据。     

浙江小黄山与河南贾湖遗址出土新石器时代前期陶器化学组成的WDXRF分析研究

利用能量色散X射线荧光光谱法(energy disperse X-ray fluorescence,EDXRF)对浙江嵊州小黄山与河南舞阳贾湖两处新石器时代前期遗址出土陶器的主量元素化学组成进行了分析测定.结果显示,这两处遗址出土陶器的化学组成地域特征明显,与贾湖遗址相比,小黄山遗址陶器具有我国南方陶瓷器普遍存在的“高...     

凌家滩遗址出土陶器的LIBS-PCA分析

采用激光诱导击穿光谱(LIBS)技术结合主成分分析(PCA),对凌家滩遗址出土陶器进行快速检测和统计分类的研究。凌家滩遗址位于安徽马鞍山市含山县,是我国南方地区一处大型新石器时代晚期聚落,遗址出土大量精美玉器、石器和陶器等,年代处于中华文明起源关键节点上,是研究我国文明起源和发展问题的重要遗址,因此对其出土陶器的研究具有十分重要的文化历史意义。对凌家滩遗址出土具有不同类型羼和料的陶器样本,进行LIBS快速分析后,利用PCA对结果进行统计辨析。研究表明,不同羼和料的光谱敏感度有所不同,不同掺杂物质会产生光谱特征差异。另一方面,出于统计分析的考虑,有目的缩小了背景噪声等异常数据干扰,并进行了分类辨析,在元素谱线归属的基础上进行了特征谱线提取,实现了利用多元统计分析进行快速分类的目的。分析结果表明,与泥质陶相比,羼植物陶器和羼细砂类样品, LIBS光谱特征具有良好的辨识度,可以进行有效区分。其他类型羼和料根据实际情况不同,则需要配合其他手段进行综合判断。相关研究结果可对南方地区新石器时期陶器的快速鉴定和类型归属等工作,提供了科学支持和有益借鉴。     

新疆巴里坤石人子沟遗址群出土玻璃珠的成分分析

巴里坤县位于新疆东部哈密地区,是连接内地与北疆的重要通道,巴里坤县境内的石人子沟遗址群是新疆东天山地区的古代游牧民族大型聚落遗址,其中西沟遗址M1墓和石人子沟遗址M011墓分别出土了一批战国晚期至西汉早期的古代玻璃珠,为了解这批玻璃珠的来源,采用激光剥蚀电感耦合等离子体发射光谱(LA-ICP-AES)和激光拉曼光谱(LRS)方法对这两批玻璃珠样品进行化学成分分析。结果表明,西沟遗址M1墓出土玻璃珠均为钠钙玻璃体系,以植物灰作为助熔剂,同时其中七件绿色玻璃珠样品均以锑酸铅作为乳浊剂;石人子沟遗址M011墓出土玻璃珠均为铅钡玻璃体系,以含铅矿物作为助熔剂。与同时期其他已经发表的玻璃数据进行比较,显示西沟遗址出土玻璃珠在成分上与美索不达米亚及古埃及钠钙玻璃不同,推测西沟遗址出土玻璃珠在中亚或新疆地区制作而成;石人子沟遗址出土玻璃珠的化学组成相对集中,应在同一地点制作而成,可能为中原地区传入。本研究证实了新疆巴里坤地区是古代东西方物质文化交流的重要节点,而游牧民族在玻璃制品传播和交流过程中扮演着重要的角色。     

浙江三个新石器时代遗址出土玉玦科技分析

玉玦是我国新石器时代广泛出现的一类重要玉器。环太湖流域新石器时代遗址中出土的大量玉玦,具有鲜明时代和地域特征,为探索中国玉文化起源和传播提供了重要实物。为获取环太湖流域新石器时代玉玦的基础材料学信息(如主要矿物组成、硬度等),以及探索玉料随时间演变规律和可能的原料来源,本文以浙江省境内3个代表性新石器时代遗址--田螺山、仙坛庙和江家山遗址出土的玉玦为研究对象,采用X射线衍射(XRD)和质子激发X射线荧光(PIXE)分析技术对其进行了无损分析检测。研究结果表明： 从河姆渡文化至崧泽文化晚期,所分析玉玦的主要组成矿物为萤石、迪开石、石英、白云母、透闪石和蛇纹石等,以萤石、玉髓和迪开石为主,且时代早于透闪石和蛇纹石。结合已有的研究成果,探讨了相关遗址出土玉玦的原料随时间变化特征、原料来源,以及玉玦的材料学特征与加工工艺之间的内在联系。     

红外光谱的煤精类文物材质判别方法

我国是世界上最早使用煤及煤精的国家之一,但对考古出土煤精文物的研究发现,煤精文物原材料的质地常常偏离宝石学中对有机宝石煤精的定义。在此提出“煤精类文物”的概念,将以往出土文物中如褐煤、烛煤等与煤精文物材质近似但不同的材料归至同一文化概念中。目前对于煤精类文物制品的科学研究仍存在较大空白,其中最为基础的材质种类判别也没有科学的判断方法。以陕西周原贺家墓地、陕西咸阳岩村墓地、新疆吐鲁番胜金店墓地、新疆伊犁吉仁台沟口遗址四个遗址出土的16件煤精制品和原料为研究对象,初步探索漫反射傅里叶变换红外光谱在出土煤精类文物成分分析中的应用。结果表明,不同遗址出土的煤精类文物的红外谱图有较为明显的不同,同一遗址出土的煤精类文物的红外谱图在特征波段具有相似性,不同遗址煤精类文物则差异明显。使用Norris二阶导数法对红外光谱进行处理,提高吸收峰分辨率,为精细研究提供信息,选择特殊红外光谱参数I=A_{820 cm-1}/A_{2 870 cm-1}定量分析不同样品的红外光谱,结合静水称重得到的部分样品的密度信息,对出土的煤精类文物制品材质的煤化程度初步判断。结合红外光谱特征波数的强度进一步通过主成分分析解释煤精类文物的红外光谱信息,来自不同遗址的煤精类文物样品在主成分分析得分图中得到了良好的区分,并且可以与特殊红外光谱参数I判别的初步结论互相对应。验证了以漫反射傅里叶变换红外光谱为主的无损分析方法在煤精类文物材质判别中应用的可行性;若结合不同产地煤精矿样红外光谱,则可以为煤精类文物产地判别提供研究方法。     

安徽枞阳出土西周至战国时期青铜器的矿料来源研究

采用激光剥蚀电感耦合等离子体质谱(LA-ICP-MS),对枞阳境内出土西周至战国时期青铜器和汤家墩遗址出土炼渣中的铜颗粒进行微量元素原位无损分析,以探讨枞阳县境内出土青铜器的铜矿来源。结果表明,枞阳汤家墩遗址冶炼铜金属颗粒中的Co,As,Sb,Ag和Bi等元素含量较高,其微量元素特征不同于铜陵和铜绿山的冶炼金属铜;从西周至战国时期,枞阳青铜器所用铜矿来源比较稳定,主要来自汤家墩遗址周边的枞阳县境内,有少量器物的铜矿可能来自长江以南的铜陵地区;LA-ICP-MS可用于青铜器和古铜矿冶遗址炼渣中所夹杂铜颗粒的微量元素原位无损分析,从而为利用炼渣探讨古矿冶遗址冶炼金属产品的微量元素特征奠定了基础,对探讨三代青铜器的矿料来源研究具有重要的应用价值。     

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.     

新石器时期西山遗址古陶器表面陶彩的分析及其与烧结温度的关系

本文应用Ｘ射线衍射仪和Ｘ光荧光光谱仪，对新石器时期河南西山遗址出土的古陶器表面的陶彩进行了分析，根据分析结果初步推断出当时陶器的烧结温度     

广西邕宁顶蛳山遗址出土黑色石料材质的光谱无损分析

石质材料鉴定是旧石器时代考古学研究的基础,因为石质种类会影响石器的制作技术、器物形态、工具类型,从而进一步制约遗址的石工业面貌乃至文化面貌。然而,仅从外观上对石器材质进行判定有很大的不确定性,特别是在鉴别黑曜石和玻璃陨石这类外观极其相似的天然玻璃质材料,大量案例表明人工目验的结果是不准确的,经常会出现误判的情况。因此,越来越多的研究开始借助现代科学仪器对石器材质进行鉴定。顶蛳山遗址作为岭南地区一处十分重要的石器时代遗址,为我们了解广西地区史前文化特征与内涵,探讨广西与周围地区史前文化交流提供了十分宝贵的资料。然而,对于出土在顶蛳山遗址中的大量黑色石器,发掘者们对这些石器的材质一直存疑。为了确定顶蛳山遗址出土黑色石料的材质,利用拉曼光谱、红外光谱和能量色散X射线荧光光谱（ED-XRF）等分析手段对其进行了原位无损材质鉴定。Raman分析表明,所有样品均为非晶态SiO₂类物质;同时样品的均在380 cm-1处出现极强吸收峰,提示样品中可能含有黄铁矿。所有样品的红外光谱在1 200~900 cm-1处平滑且不见明显肩峰,同时在750~500 cm-1处不见明显吸收峰,表明样品不含斜长石、石英等矿物,这与玻璃陨石的物相特征相吻合。ED-XRF结果表明,样品的主要成分是SiO₂和Al₂O₃,且其碱土金属（RO）和铁含量高而碱金属含量低（R₂O）,R₂O/RO小于1、K₂O/CaO的比值处于0.8～1.6之间,这些成分特征均与玻璃陨石相符。综合以上分析结果,可确定本文分析的石料样品均是玻璃陨石。分析结果对于进一步探讨顶蛳山遗址出土黑色石料的产地,顶蛳山遗址先民的活动范围及其与周边地区史前文化的交流与互动都具有重要参考价值。     

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.     

平顶山应国墓地出土原始瓷的制作工艺和产地

原始瓷一直是学术界所关心的重要问题,其产地和工艺关系到我国古代陶瓷发展模式以及商周文化面貌研究,具有十分重要的学术价值。采用XRF和XRD等科技手段,对最新出土的河南平顶山应国墓地遗址7枚原始瓷片进行了测试和产地推测。分析结果显示,应国墓地原始瓷瓷釉中磷含量明显偏高,暗示其使用了草木灰作为原料。与其他已发表的原始瓷数据相比,应国墓地出土原始瓷瓷釉的Ca/Al和P/Al值明显不同,暗示其配方工艺与南方产地产品有所差别。分析结果显示,应国墓地原始瓷产地不在南方。     

Surface analysis in archaeology using the miniaturized Mössbauer spectrometer MIMOS II

We report on an interdisciplinary study of ceramic material excavated in 1999 and 2001 at a 1000-year old ceramic and metal production site, located at Huaca Sialupe in the La Leche valley on the north coast of Peru and dating to the Middle Sicán period (AD 900–1100). Sherds of Sicán red- and blackware, numerous moulds, several kilns and other evidence of pottery making were found. The pottery, in particular, is famous for its fine texture and perfect black surface finish. In addition, some clay lumps and sherds of unfired Sicán pottery were excavated. Within the same workshop several large inverted ceramic urns used as furnaces were found together with Middle Sicán metal working tools and debris. Various physical methods were applied to investigate this material. The ancient firing procedures could be elucidated by comparing the spectra observed for the ancient sherds with model spectra of laboratory and field fired clay samples. This shows that the fine ware made at Huaca Sialupe was intentionally fired under strongly reducing conditions at temperatures up to 900°C. Reoxidation at the end of the reducing firing took place only occasionally. Less care was taken in firing moulds used for pottery making.     

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.     

庙底沟遗址出土仰韶文化彩陶的科学研究

彩陶文化作为新石器时期的重大发明,改变了远古先民的审美方式,而著名的仰韶文化以其彩陶的优美造型、绚丽色彩和丰富的纹饰揭示了原始的艺术特征,承载了史前时期重要的社会文化信息。而利用现代光谱分析技术准确、无损和微损的特点,可以为文物保护的研究提供更科学的技术支撑。研究应用相位辅助光学三维扫描、多光谱成像、X射线荧光、激光拉曼光谱分析技术,对河南省陕县庙底沟遗址出土的新石器时代晚期仰韶文化彩陶碗进行面、点相结合的综合分析,获得了较为完整的文物物理和化学信息。利用三维扫描技术所构建的彩陶碗数字化模型对样品进行了几何尺寸的非接触测量和虚拟修复,利用多光谱成像技术所获得的灰度图像对样品表面化学特征相似区域进行了区分,结合X射线荧光和激光拉曼光谱分析技术对彩陶残片的分析结果,确定了所分析彩陶样品的主要化学成分特征和颜料物相组成。综合研究结果,提出了建立彩陶文物多源信息数字化模型的构想,为这类文物的数字化保护和展示提供了基础科学信息。     

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.     

成都金沙遗址古代陶片的PIXE和RBS分析(英文)

成都金沙遗址的年代覆盖了商代晚期至西周时期（公元前1200年—公元前650年）, 一般被认为是三星堆文化的延续。初步建立了质子激发X射线发射（PIXE）和卢瑟福背散射（RBS）实验装置, 并采用PIXE和RBS方法研究了从金沙遗址出土的部分陶片的元素组成。通过因子分析, 观察到来自不同地层的陶片的元素组成存在一定的差异, 这可能意味着制作陶器的陶土在不同时期取自不同的地点。也观察到来自不同发掘坑的陶片的元素组成没有明显的聚类现象, 这可能意味着制作不同使用用途的陶器所用的陶土是没有区别的。Jinsha Ruins Site, Chengdu, China, spanned the age from late Shang Dynasty to Western Zhou Dynasty (B.C.1200—B.C.650), was generally considered as the inheritance of Sanxingdui Culture. This paper focuses on the studies of the pottery unearthed from Jinsha. PIXE and RBS experimental setup was preliminarily established and these techniques were employed to find the elemental composition of those collected shards. From the results of factor analysis, the differences can be seen among pottery shards from different stratums, which may suggest that the clay gathered from different sites was used in different periods. The authors also found that there was no obvious assemblage phenomenon in the factor analysis among the pottery shards from different pits, this may be the evidence for “no special clay for special use”.     

Chemical cleaning of encrustations on archaeological ceramic artefacts found in different Italian sites

With the aim of contributing to the knowledge of north-Mesopotamian Bronze Age pottery production (3rd millennium BC, early Dynastic and early Akkadian period), the mineralogy of pottery excavated from the site of Tell Beydar (Syria) has been studied in order to make inferences concerning the clay preparation and firing techniques of that period. The fired pottery finds have been classified by archaeologists into three distinct groups on the basis of their aesthetic and visual appearance and their mechanical strength: standard, cooking and “metallic” ware. SR X-ray powder diffraction data have been collected from 100 individual shards as well as from local clays and one unbaked object, an inscribed tablet. The XRD data is supplemented by SEM-EDS, XRF and polarising microscopy studies of 200 polished thin sections. The synthesis of the results from this extensive study quantifies the basic physical characteristics of the ensemble: the standard ware required no specific clay preparation and firing procedures. The body of the cooking ware contains large inclusions which result in a body texture intended to make them resistant to repeated thermal cycles. Both standard and cooking ware are made of a calcareous clay, typical of pottery from the Middle East. The metallic ware, however, are of a much finer quality with a distinctly different mineralogy than the other two groups. PACS 81; 81.05.Je; 81.05.Mh; 82.80.Ej     

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.