Early globalized industrial chain revealed by residual submicron pigment particles in Chinese imperial blue-and-white porcelains.

The success of early Chinese blue-and-white porcelains relied heavily on imported cobalt pigment from the West. In contrast to art-historical concept, which contains both typological evidence and literature records, it is assumed that imported Sumali blue was completely superseded by domestic Chinese asbolane ore based on the analytical results of the Fe/Mn ratio in imperial productions from the Xuande reign (1426 to 1435 CE) onward. Using a focused ion beam transmission electron microscopy technique to reassess this hotly debated question, we have identified two classes of residual submicron pigment particles in the blue glaze with diagnostic differences in morphology, chemical composition, and distribution behavior. Compared with the microstructural features of the blue-and-white porcelains of the Yuan and Qing dynasties, we show that a mixture of imported and domestic cobalt pigments was used for aesthetic reasons, indicating that the overseas supply chain of imported pigment remained consistent and adequate even though the authorities had terminated official trade and tributary activities after the death of Admiral Zheng He. This discovery further suggests that the globalized trading network and cross-regional industrial chain had been extensively established in the 15th century. Moreover, we provide analytical evidence against the fundamental assumption of the current Fe/Mn provenancing criteria, implying that the failures of previous chemical analyses can be attributed to elemental differentiation between the silicate glaze and the arsenic pigment. We propose an innovative method for directly assessing original mineralogic information from submicron residual pigment particles that provides a more reliable way to trace cobalt circulation and holds great promise for provenance studies.

Earliest evidence for commensal processes of cat domestication.

Domestic cats are one of the most popular pets globally, but the process of their domestication is not well understood. Near Eastern wildcats are thought to have been attracted to food sources in early agricultural settlements, following a commensal pathway to domestication. Early evidence for close human-cat relationships comes from a wildcat interred near a human on Cyprus ca. 9,500 y ago, but the earliest domestic cats are known only from Egyptian art dating to 4,000 y ago. Evidence is lacking from the key period of cat domestication 9,500-4,000 y ago. We report on the presence of cats directly dated between 5560-5280 cal B.P. in the early agricultural village of Quanhucun in Shaanxi, China. These cats were outside the wild range of Near Eastern wildcats and biometrically smaller, but within the size-range of domestic cats. The δ(13)C and δ(15)N values of human and animal bone collagen revealed substantial consumption of millet-based foods by humans, rodents, and cats. Ceramic storage containers designed to exclude rodents indicated a threat to stored grain in Yangshao villages. Taken together, isotopic and archaeological data demonstrate that cats were advantageous for ancient farmers. Isotopic data also show that one cat ate less meat and consumed more millet-based foods than expected, indicating that it scavenged among or was fed by people. This study offers fresh perspectives on cat domestication, providing the earliest known evidence for commensal relationships between people and cats.

Colouration mechanism of underglaze copper-red decoration porcelain (AD 13th-14th century), China.

Underglaze copper-red decoration, i.e. the copper colourant used to paint diversified patterns on the surface of a body and then covered by transparent glaze and fired at high temperature in a reductive firing environment, is famous all over the world. However, the red colouration mechanism generated by underglaze copper remains unclear. In particular, the fact that the edges of the red patterns are orange has been ignored in previous research. Here, non-destructive analysis has been carried out on a precious fragment of early underglaze red porcelain using synchrotron radiation X-ray fluorescence, X-ray absorption near-edge spectroscopy (XANES) and reflection spectrometry techniques. The results suggest that the copper content in the red region is higher than that in the orange region, and other colour generation elements do not have obvious content difference, indicating that the colour generation effect of the underglaze red product is related to the copper content. XANES analysis shows that the valence states of copper in the red and orange regions are similar and metal copper contributes to their hues. The results of reflection spectrometry demonstrate that tiny orange hues could be attributed to the Mie scatting effect. Therefore, light-scattering effects should be considered when researching the colouration mechanism of underglaze red.

Nondestructive analysis of dragonfly eye beads from the warring states period, excavated from a Chu tomb at the Shenmingpu site, Henan Province, China.

Dragonfly eye beads are considered to be the earliest types of glass objects in China, and in the past have been considered as evidence of culture interaction or trade between West and East Asia. In this article, synchrotron radiation microcomputed tomography and µ-probe energy dispersive X-ray fluorescence were used to determine the chemical composition, microstructure, and manufacturing technology of four dragonfly eye beads, excavated from a Chu tomb at the Shenmingpu site, Henan Province, China, dated stylistically to the Middle and Late Warring State Period (475 BC-221 BC). First, a nondestructive method was used to differentiate the material types including faience (glazed quartz), frit, glazed pottery (clay ceramic), and glass. Three beads were identified as faience and one bead as glazed pottery. The glaze recipe includes quartz, saltpeter, plant ash, and various copper, and is classified as belonging to the K2O-CaO-SiO2 glass system, which indicates that these beads were not imported from the West. Based on computed tomography slices, the manufacturing technology of the faience eye beads appears to include the use of an inner core, molding technology, and the direct application glazing method. These manufacturing features are consistent with the techniques used in China during this same time period for bronze mold-casting, proto-porcelain, and glass.

[Raman microspectroscopic analysis of polychrome wooden artifact from the Astana tomb of the tang dynasty, Xinjiang, China].

The Turpan District is characterized by a typical dry climate, so that many organic relics have been well preserved. A piece of wooden artifact with 9 colors was unearthed from Astana graveyard which is rich in cultural connotations. In the present paper, Raman microscopy was employed for in-situ, nondestructive analysis of pigments that remained on this artifact, and many mineral pigments (gypsum, red lead, carbon black, haematite, atacamite) and vegetable dyes (gamboges and indigo) were identified. It is noteworthy that this is the earliest example that gamboges were used as yellow dye in China at present. The results show that the Gaochang people had mastered skills proficiently, including the preparation, deployment and usage of pigment. The investigation of pigments could provide a basis for the restoration and conservation of relies, and more evidence for pigments trade business and cultural exchanges.

Stable isotope dietary analysis of the Tianyuan 1 early modern human.

We report here on the isotopic analysis of the diet of one of the oldest modern humans found in Eurasia, the Tianyuan 1 early modern human dating to approximately 40,000 calendar years ago from Tianyuan Cave (Tianyuandong) in the Zhoukoudian region of China. Carbon and nitrogen isotope analysis of the human and associated faunal remains indicate a diet high in animal protein, and the high nitrogen isotope values suggest the consumption of freshwater fish. To confirm this inference, we measured the sulfur isotope values of terrestrial and freshwater animals around the Zhoukoudian area and of the Tianyuan 1 human, which also support the interpretation of a substantial portion of the diet from freshwater fish. This analysis provides the direct evidence for the consumption of aquatic resources by early modern humans in China and has implications for early modern human subsistence and demography.

A new 3D information acquisition method of micro-drilling marks on ancient perforated stone bead through micro-CT.

Drilling is one of the most complex techniques for making ancient stone or jade implement or adornment. However, related research on ancient stone or jade drilling technology lags behind, for there are rare records or discovery of the ancient drilling tools. Drilling marks are very useful information for analysis and research of the ancient drilling techniques. The traditional information acquisition methods are very difficult to apply effectively on smaller perforations. In this paper, we introduced a new nondestructive method to solve the observation difficulty problem. The ancient bead was scanned by 3D-µCT system. Then through T-FDK algorithm, improved NL-means denoising algorithm and high accurate calibration, the 3D geometrical information of micro-drilling marks on outer and inner wall of the perforation were reconstructed. The experimental results proved that this method can provide key information for the analysis of the ancient stone drilling technique and ancient jade authentication.

[Technology and provenance of proto-porcelain of Yingguo graveyard in Henna province].

Protoporcelain is a kind of multi-epoch and multi-culture-area ceramic hangover with iterative appearance, and it is the important interim of the development from pottery to porcelain. Therefore, its origin, development and prevalence problems, which relate directly to China development mode and Shang Zhou culture visage, are the important discussion of archaeology, ceramic technic history and chemistry history, and have important learning value. XRF and XRD technique were used to determine several shreds excavated from Yingguo graveyard site in Henan province. The result shows that some samples have abnormity phosphor, hinting that some plant or wood ash was ever used as raw material. From the rate of Ca/Al and P/Al and comparative analysis, we discovered that proto-porcelain of Yingguo site has different chemical character compared to south production.

[Identification of different corrosion covering the surface of Chinese ancient lead glazed potteries].

In the present paper, different corrosions of three pieces of Chinese ancient lead glazed potteries from different burial circumstances were analyzed by using XRD, FTIR, EDXRF, RS etc, and the analyses indicate that the main crystalline phase of corrosion of HYT is cerussite (PbCO3), that of SYT is calcium-lead hydroxyapatite [Pb(10-x) Ca(x) (PO4)(OH)2 (x < 2.7)] and the yellow area of the erosion is attributed to a certain mount of iron oxide, that of TSC is the cerussite (PbCO3) and calcium-lead hydroxyapatite [Pb(10-x)Ca(x) (PO4) (OH)2 (x < 2.7)], and the brown-black area of the erosion product is the result of the existence of little mount of iron and carbon black.

Tianshanbeilu and the Isotopic Millet Road: reviewing the late Neolithic/Bronze Age radiation of human millet consumption from north China to Europe.

The westward expansion of human millet consumption from north China has important implications for understanding early interactions between the East and West. However, few studies have focused on the Xinjiang Uyghur Autonomous Region, the vast geographical area directly linking the ancient cultures of the Eurasian Steppe and the Gansu Corridor of China. In this study, we present the largest isotopic investigation of Bronze Age China (n = 110) on material from the key site of Tianshanbeilu, in eastern Xinjiang. The large range of δ13C values (-17.6‰ to -7.2‰; -15.5 ± 1.2‰) provides direct evidence of unique dietary diversity and consumption of significant C4 resources (millets). The high δ15N results (10.3‰ to 16.7‰; 14.7 ± 0.8‰) likely reflect sheep/goat and wild game consumption and the arid climate of the Taklamakan Desert. Radiocarbon dates from four individuals indicate Tianshanbeilu was in use between 1940 and 1215 cal bc. The Tianshanbeilu results are then analysed with respect to 52 Bronze Age sites from across Eurasia, to investigate the spread and chronology of significant human millet consumption and human migration. This isotopic survey finds novel evidence that the second millennium bc was a dynamic period, with significant dietary interconnectivity occurring between north China, Central Asia and Siberia. Further, we argue that this 'Isotopic Millet Road' extended all the way to the Mediterranean and Central Europe, and conclude that these C4 dietary signatures of millet consumption reflect early links (migration and/or resource transfer) between the Bronze Age inhabitants of modern-day China and Europe.

Raman analysis of cobalt blue pigment in blue and white porcelain: A reassessment.

Cobalt blue is a famous pigment in human history. In the past decade it is widely reported that the cobalt aluminate has been detected in ancient ceramics as blue colorant in glaze, yet the acquired Raman spectra are incredibly different from that of synthesised references, necessitating a reassessment of such contradictory scenario with more accurate analytic strategies. In this study, micro-Raman spectroscopy (MRS) and scanning electron microscopy (SEM) in association with energy dispersive spectrometry (EDS) were performed on under-glaze cobalt pigments from one submerged blue and white porcelain shard dated from Wanli reign (1573-1620CE) of Ming dynasty (1365-1644CE) excavated at Nan'ao I shipwreck off the southern coast of China. The micro-structural inspection reveals that the pigment particles have characteristics of small account, tiny size, heterogeneously distribution, and more importantly, been completely enwrapped by well-developed anorthite crystals in the glaze, indicating that the signals recorded in previous publications are probably not from cobalt pigments themselves but from outside thickset anorthite shell. The further spectromicroscopic analyses confirm this presumption when the accurate spectra of cobalt aluminate pigment and surrounding anorthite were obtained separately with precise optical positioning. Accordingly, we reassess and clarify the previous Raman studies dedicated to cobalt blue pigment in ancient ceramics, e.g. cobalt blue in celadon glaze, and in turn demonstrate the superiority and necessity of coupling spectroscopic analysis with corresponding structure observation, especially in the characterization of pigments from complicated physico-chemical environment like antiquities. Thus, this study promotes a better understanding of Raman spectroscopy study of cobalt blue pigments in art and archaeology field.

Open sesame: Identification of sesame oil and oil soot ink in organic deposits of Tang Dynasty lamps from Astana necropolis in China.

Lamp illuminants evidence the exploitation of natural resources, animal and plant domestication, commerce, religious practices and nutrition of ancient populations. However, the physicochemical analysis of their major constituent-burned, degraded and aged mixture of triacylglycerols is imprecise and may lead to ambiguous interpretations. We applied proteomics to analyze fuel deposits from eight lamps dated by 6th to 8th centuries AD that were excavated at the Astana necropolis (Xinjiang, China) and determined their origin by identifying organism-specific proteins. Proteomics evidence corroborated and detailed the assignments of source organism relying upon comparative profiling of intact triacylglycerols by shotgun lipidomics. We found that ruminant (mostly, sheep) fat, cattle ghee and sesame oil were common combustibles in Astana and concluded that sesame as an oilseed appeared in China under Tang Dynasty concomitantly with the expansion of Buddhism.

[Study on colored drawing technique of Qionglai kiln by SRXRF].

The colored drawing technique of Qionglai kiln is a debate problem in the archaeology and ancient ceramic research. In the present paper, SRXRF linescan technology was used to study the distribution mode of the colorific elements on the cross-sections of samples. The analytical result indicates that there existed two kinds of decoration techniques of colored drawing, i. e. the techniques of the underglaze color and oveglaze color coexisted in that time.

[Linear scanning analysis of prehistoric human bones in Xigongqiao Site, Tengzhou, Shandong Province by use of SEM-EDS].

Ancient human bones in Xigongqiao Site, Tengzhou, Shandong Province, were analyzed by use of SEM-EDS. SEM indicated that the microstructure of Haversian system was destroyed under the impact of bone diagenesis. The apparent difference in elemental distribution in the bone cross section showed that the enrichment or loss of elements can occur not only in the inner and outer surface, but also in the middle. This study will have great influence on how to deal with the ancient human bones before any palaeodietary research in the future.

Investigating the tool marks on oracle bones inscriptions from the Yinxu site (ca., 1319-1046 BC), Henan province, China.

Oracle Bone Inscriptions in the Shang dynasty (1600-1046 BC) are the earliest well-developed writing forms of the Chinese character system, and their carving techniques have not been studied by tool marks analysis with microscopy. In this study, a digital microscope with three-dimensional surface reconstruction based on extended depth of focus technology was used to investigate tool marks on the surface of four pieces of oracle bones excavated at the eastern area of Huayuanzhuang, Yinxu site(ca., 1319-1046 BC), the last capital of the Shang dynasty, Henan province, China. The results show that there were two procedures to carve the characters on the analyzed tortoise shells. The first procedure was direct carving. The second was "outlining design," which means to engrave a formal character after engraving a draft with a pointed tool. Most of the strokes developed by an engraver do not overlap the smaller draft, which implies that the outlining design would be a sound way to avoid errors such as wrong and missing characters. The strokes of these characters have different shape at two ends and variations on width and depth of the grooves. Moreover, the bottom of the grooves is always rugged. Thus, the use of rotary wheel-cutting tools could be ruled out. In most cases, the starting points of the strokes are round or flat while the finishing points are always pointed. Moreover, the strokes should be engraved from top to bottom. When vertical or horizontal strokes had been engraved, the shell would be turned about 90 degrees to engrave the crossed strokes from top to bottom. There was no preferred order to engrave vertical or horizontal strokes. Since both sides of the grooves of the characters are neat and there exists no unorganized tool marks, then it is suggested that some sharp tools had been used for engraving characters on the shells. Microsc. Res. Tech. 79:827-832, 2016. © 2016 Wiley Periodicals, Inc.

Characterization of cosmetic sticks at Xiaohe Cemetery in early Bronze Age Xinjiang, China.

Cosmetics have been studied for a long time in the society and culture research, and its consumption is regarded as a cultural symbol of human society. This paper focuses on the analysis of the red cosmetic sticks, found in Xiaohe Cemetery (1980-1450BC), Xinjiang, China. The structure of the red cosmetic sticks was disclosed by SR-µCT scanning (Synchrotron Radiation Micro-computed Tomography), while the chemical components were characterized by FTIR (Fourier Transform Infrared Spectroscopy), Raman Spectroscopy and Proteomics. The results suggested that the cosmetic sticks were made from the cattle heart and covered with a layer of hematite powders as the pigment. Given the numerous red painted relics in Xiaohe Cemetery, this kind of cosmetic sticks might be used as a primitive form of crayon for makeup and painting. The usage of cattle hearts as cosmetic sticks is firstly reported up to our knowledge, which not only reveals the varied utilizations of cattle in Xiaohe Cemetery but also shows the distinctive religious function. Furthermore, these red cosmetic sticks were usually buried with women, implying that the woman may be the painter and play a special role in religious activities.

[Line scanning analysis of white porcelain from Gong Kiln in early Tang dynasty by energy disperse X-ray fluorescence].

Gong kiln, for its long porcelain-firing history, was one of three representative white porcelain kilns in northern China. In order to improve the quality and whiteness of white porcelain, a decorating layer or cosmetic earth was laid on the body surface in Gong kiln during early Tang dynasty, which was able to blot out rough surface and weaken the influence of fuscous body upon surface color. In this paper the main chemical composition of the white porcelain's profile was analyzed by using energy disperse X-Ray fluorescence. The result showed that different materials were used as cosmetic earth during early Tang dynasty, in accordance with the phenomenon under optical microscope. In addition, the glaze belongs to calcium glaze in which plant ash was added.

[Application of Raman spectra to the research of jades excavated from Xue Jiagang site].

Non-destructive analysis is always the aim in jades' research. The present article applied the Raman spectroscopy to the research on jades excavated from the Xue Jiagang site and achieved good result in the main mineral, inclusion and phenocryst. The study shows that as a non-destructive technique Raman spectroscopy can be applied to ancient jades conveniently and practically, and it can detect not only the surface information of ancient jades, but also the interior information. The technique is important to the verification and provenance of ancient jades.

[The application of trace element analysis to the study of provenance of copper minerals in ancient bronzes].

The simulated smelting and founding experiment of bronze showed that the copper minerals from different regions could be distinguished clearly by using the multi-statistical analysis based on choosing the chalcophile elements determined by ICP-AES. In the present paper, the data of trace elements in bronzes from Panlongcheng Site and Ezhou, which were determined by NAA, were tried to be processed. The analytical result showed that the bronzes from Panlongcheng and Ezhou could be divided clearly, just like the results of the former simulated smelting and founding experiment of bronze. So, the feasibility of trace element analysis for the study of provenance of copper minerals in ancient bronzes was proved again.

[Plane scan analysis of the surface of white and blue porcelain by SRXRF method].

In this article, the authors analyze the surface of a piece of porcelain shred in Xuande Period by SRXRF, and the result shows that each peak area of elements differs in distribution pattern. According to the relationship between element peak area and color variation, and yellow fleck in glaze, it is possible to divide 13 elements, i.e. K, Cr, Mn, Fe, Co, Ni, Cu, Zn, Hg, Rb, Sr, Y and Zr, into three groups. This phenomenon will indicate how to search the "finger elements" in each dynasty; at the same time, it will present important information for research on the forming mechanism of yellow flecks in glaze.