Turquoise-inlaid composite ornaments are commonly found in Late Neolithic and Bronze Age China. However, the methods used to affix small turquoise pieces to prehistoric ornaments remain unclear. In this study, archaeological adhesive samples from turquoise-inlaid wrist ornaments found at the Taosi site, Shanxi Province, north China, during 2300 − 1900 BCE, were characterized by using FTIR and Py-GC/MS analysis. Through comparing the chemical compositions of archaeological materials and modern samples, the adhesive was identified as birch bark tar, which is reported for the first time in China. Moreover, it is also suggested that the wide use of turquoise inlaying technology in north China may be linked to the production of birch bark tar. This research has combined chemical analytical technologies with archaeological background information to reconstruct the technological development and material innovation in ornamental manufacturing of early societies in ancient China.
The characterization of dyes in archaeological textiles traditionally relies on laboratory-based analytical techniques that are often time-consuming and involve extensive sample preparation. In this study, a dye database based on a miniaturized ion trap mass spectrometer coupled with an ambient ionization source is firstly established and then applied to the rapid analysis of ancient silk textiles from archaeological contexts. The results provide chemical evidence for a traditional Chinese purple dyeing combination including ellagic acid, shikonin, and alizarin possibly with berberine during the Xizhou period of the Tang Dynasty (640-795 CE) at Astana Cemetery, Turpan Basin, northwest China. This study further demonstrates the potential of portable ion trap mass spectrometry system for rapid dye characterization in cultural heritage applications. Compared with conventional laboratory-based methods, the approach offers advantages in portability and analytical flexibility, making it particularly suitable for fragile or high-value archaeological textiles and on-site analysis. The establishment of the reference library provides a foundation for improving the consistency of dye identification across different materials and historical contexts. These results highlight the applicability of portable ion trap mass spectrometry system as a complementary tool for the molecular investigation of ancient dyeing practices.
Plant fibers are the core raw materials of traditional East Asian handmade papers. For their identification, microscopic observation has been conventionally conducted relying on fiber staining combined with optical microscopy. Comparatively, polarized light microscopy (PLM) has long been underutilized, especially in the study of ancient East Asian paper relics. Thus, this study aims to evaluate the feasibility of PLM in characterizing fiber optical properties and identifying morphological features, which can be used to distinguish bast fibers in traditional Chinese handmade paper production. As a result, the differences in microfibril angle (MFA) and the effects of alkali treatment on the samples suggest that color changes in the sign of elongation (SE) can serve as indicators for fiber evaluation and characterization, though nuance differences await further exploration. Methodologically, the cross-polarized light (CPL) mode detects optical characteristics (SE and Herzog tests), while the single-polarized light (SPL) mode captures morphological details. This combined approach can effectively distinguish different papermaking bast fibers, offering a micro-destructive technique for identifying plant fibers in East Asian handmade papers and fibrous relics in antiquity.
During the Han Dynasty, cosmetic production flourished, as evidenced by archeological discoveries of numerous lacquer toiletry cases across China. However, the use of cosmetics by non-elite populations has received comparatively little attention. Here, a cosmetic residue from a non-elite Han tomb at the Kongwangshan site on the southern margin of the North China Plain was analyzed using SEM-EDS, FTIR, XRD, GC-MS, HS-SPME-GC-MS, and GC-C-IRMS. The results indicate that the formulation consists of finely ground mica, plant-derived ingredients, and non-ruminant animal fat, likely of porcine origin. Integrating data on container typology, formulation composition, historical and archeological contexts, we postulate that cosmetics, once largely restricted to elite groups during the pre-Qin period, had become increasingly accessible to broader social strata by the Han Dynasty. This reflects wider economic development, expanding craft production, and changing consumption practices, providing new insights into the socio-economic dynamics of early imperial China.
The Tibetan Plateau presents an extreme natural environment, yet how prehistoric populations entered and adapted to high-altitude settings, and how subsistence strategies emerged and transformed in this process, remain poorly understood. Using the newly discovered Yansha site (YS) as a focal case, we integrate chronometric dating, analyses of lithics, combustion-related sediments, and faunal remains with the Living Environment Suitability Index (LESI), potential mobility corridor analysis, and the Agricultural Suitability Index (ASI) to investigate patterns of human activity and land-use change on the Plateau from the last deglaciation to the middle and late Holocene (15-4 ka). Results show repeated occupations at YS between 13.3 and 8.1 ka, with their chronological distribution broadly consistent with changes in environmental suitability, whereas no clear evidence of human activity was identified during the cold-dry Younger Dryas. At the regional scale, microlithic activity was concentrated in suitable areas along the eastern and northeastern margins of the Plateau and organized along potential mobility corridors following river valleys and lake-basin zones, with the northeastern, eastern, and southeastern route zones forming a spatial structure linking the Plateau periphery with its interior. The YS site lies near the Huangshui River-Qinghai Lake-Hala Lake corridor and corresponds closely to modelidentified mobility pathways. During 8-4 ka, agricultural potential was concentrated along the eastern Plateau margin and adjacent low-elevation valleys, whereas the YS area remained a low-suitability fringe. Overall, the YS site provides micro-scale evidence for understanding human activity patterns along the northeastern margin of the Tibetan Plateau from the last deglaciation to the early Holocene.
ABSTRACT The jade inlays on bronze artifacts were popular in southwest China during the late Bronze Age. However, the identification of the adhesives employed is limited. At the Dayuanzi Cemetery, located in Shizong county, there are many bronze bracelets and decorative buttons inlaid with numerous small malachite beads and/or white agate. In this study, black and white adhesive samples were collected from 18 bronzeware and characterized through Fourier transform infrared spectroscopy, gas chromatography–mass spectrometry and pyrolysis–gas chromatography/mass spectrometry. Plant white wax from Chinese tallow tree seeds is also analyzed for comparison. The results reveal that the black adhesives are mainly made of drying oils, and the white adhesives should be a kind of insect white wax, but not traditional Chinese wax. This finding is the earliest chemical evidence of exploiting insect white wax in China. This study provides essential background information and a foundational understanding of bronze decoration craftsmanship and contributes to future preservation and restoration efforts.
Ancient paper artifacts in China are exceedingly rich, encompassing a variety of ancient papers from different historical periods, including the Han Dynasty (202 BC-220 AD) to the Qing Dynasty (1644-1911 AD). The Dove Cave site, located approximately 200 km north of Beijing in Longhua ((sic)(sic)) county, has unearthed paper fragments dating to the late Yuan Dynasty (Yuan Dynasty, 1271-1368 AD; the latest date of the site's documents is 1362 AD). This was the first systematic archaeological excavation of ancient papers in areas surrounding the metropolis of Beijing, providing valuable samples for understanding papermaking and paper usage in the late fourteenth century in northern China. With aims to decode its manufacturing crafts, this study was carried out via SEM-EDS, FTIR, and Py-GC/MS to investigate the utilization of papermaking fibers and the composition of sizing reagents. The results revealed that the paper fragments utilized paper mulberry and hemp fibers and were treated with egg white as sizing glue, a first discovery and report of such sizing agent in ancient Chinese handmade paper treatment. As a result, through the micro-damage analysis for the conservation and research of paper artifacts, a deeper understanding of the raw materials and manufacturing processes of ancient paper was obtained, which provides additional insights for substantiating the development of ancient papermaking.
RATIONALE:Morphological analysis has been frequently applied in archaeobotany. Recently, increasing studies have been conducted on the identification of biomarkers in archaeobotanical materials, which are rarely attached to morphological analysis. To improve the interpretability of biomarker analysis, the localisation of characteristic biomarkers in ancient samples is needed. METHODS:We analysed characteristic lignans in ancient/modern sesame seeds via matrix-assisted laser desorption ionisation quadrupole time-of-flight mass spectrometry imaging (MSI), testifying the potential of MSI in a detailed discussion of ancient plant use practices. RESULTS:The MSI distributions of sesamin and sesamolin shared similar traits in modern and ancient sesame seeds while their MSI signals were inhibited by lipidic substances in in situ MSI tests. Besides targeted biomarker characterisation, nontargeted MSI analysis showed potential to reveal plant material treatment process. CONCLUSIONS:Botanical biomarker distribution traits were studied for the first time in archaeobotany. The MSI created a visualised colour plot with localised compound distributions, in which archaeologists can visually aid their study of plant use in antiquity. This, in some cases, provides key information for understanding the livelihoods of ancient people.
The Song dynasty (970-1279 CE) was an era of a prosperous commodity economy, culture and education in China history, with various descriptions of cosmetic usage. However, archaeological evidence for cosmetic application during this period was rare, which hindered comprehensive understanding. During the excavation of the Shijiatang cemetery, two small and exquisite porcelain containers with suspected cosmetics were unearthed from tomb M50, which belonged to a female with an established social position. In this study, ATR-FTIR, SEM, GC/MS, Py-GC/MS and GC-C-IRMS were used to characterize the residue inside the container, and the results demonstrate that the residue is made of minerals, non-ruminant animal adipose fat and plant ingredients. In particular, the detection of arundoin and cylindrin indicates that the herbal medicine plant Bai Mao (Imperata cylindrica) was likely used as a cosmetic ingredient by the noble class of the Song dynasty. This study provides a precious example of cosmetic production in the Song dynasty and, together with the prevalence of cosmetic use described in historical records, suggests a boom in the cosmetics industry during that period. Furthermore, the exploitation of natural herbal ingredients reflects a master of herbal knowledge and a trend to use natural products to aid in maintaining beauty.
Background Pottery lipid residue analysis has been extensively practiced worldwide as an important part of archaeometry studies, but in some cases, the complexity of archaeological residue cannot be fully revealed by one-dimensional gas chromatography (1D GC) separation. Although the development of comprehensive two-dimensional gas chromatography (GCxGC) has offered another way to achieve better separation and higher resolution, GCxGC separation has rarely been applied to pottery residue analysis. Clearly, GCxGC separation needs to be explored to examine and scrutinize the complexity of pottery lipid residue profile as well as rapid data treatment workflow. Results We analyzed pottery residue via comprehensive gas chromatography/mass spectrometry (GCxGC/MS), through which a thorough understanding and deeper insight into their constituent complexity were obtained. The merits of GCxGC/MS separation were illustrated by a structured layout of different series of compounds on a 2D contour plot, with a detailed examination of the distributions of linear and branched fatty acid methyl esters (FAMEs) congeners, dimethyl esters (DIMEs) congeners and ω-(o-alkylphenyl)alkanoic acids (APAA) congeners with similar structures. The results showed that 2D analysis increased the number of chemical signatures, especially those at a trace level, which can be favorable for fingerprinting and identification. Additionally, the ordered group featured layout in the 2D profile leads to easy and quick location and identification of compound series as well as individual compounds, together with the use of high-quality mass spectra, facilitating a more rapid and reliable identification workflow. The improved characterization of aquatic biomarkers such as APAAs provides a more detailed discussion of ancient aquatic culinary and dietary practices. Significance The complexity of isomerism and the number of congener patterns within pottery residues are illustrated for the first time, and 2D separation is beneficial for the analysis of pottery residues as well as other complex archaeological residues in cultural heritage and archaeological research. The 2D analysis built a visualized color plot with a structured layout of different compound series that simplified the analysis workflow, in which the archaeologist can visually compare the complexity of the sherd residue not attainable in the 1D analysis workflow. The improvement in sensitivity also enables the detection of trace-level compounds, which, in some cases, constitute key information in ancient diet studies.
ln recent decades anc ent parchment study has rece ved much attent on A though the number of i parchment studies has increased, there is currently no bib liometric perspective addressing this topic. The purpose of this study was to analyse the intellectua l base and academic research frontier using C iteSpace , a b ib liometr ic v isua lisat ion and ana lys is software . We retr ieved 164 art ic les pub lished in print or online as early-access articles between 2008 and 2023 from the Web of Science through a , topic search related to parchment. Then, we analysed synthesised networks of co-authorship , , (authors, institutions, countries), co-citation (authors, documents, journals), and co-occurring keywords were analysed. The annua l publication output has trended upward since 2008. Authors , , based in Italy accounted for 29.3% of the tota l publications, followed by England (16.5%), and overall, publications from Europe were the most influentia l. Such evidence also hints at the historical , trajectory of the spread and use of parchments. Based on keyword analysis, micro-Raman , , spectroscopy, Paleolithic bone surface microtopography, European cultura l heritage, non-invasive molab investigation and art forgeries are among the most studied methods. The major research themes identified included the characterisation of parchment samples using spectroscopic techniques, the ageing mechanism and protection of parchment paper, the conservation and anti- counterfeiting of cultura l heritage objects. Emerging themes included proteomic studies and molecular biology analysis. It is foreseeable that future research on parchment or even cultural , heritage w ill be characterised by the tendency toward non-destruction and digitalisation, as we ll as multidisciplinary intersection and parallelism of multiple means to deepen our understanding of ancient parchment.
Folk contract documents (FCD) are valuable materials for studying social history, and the paper they use reflects the social realities of different eras and social classes. Research and scientific analysis of numerous FCD samples after the fourteenth century are rare. We conducted a study on 96 Tianshui folk contract documents (TFCD, 107 paper samples) from the Tianshui area of Gansu Province, Northwest China, taking into account both the textual content and the materiality of paper carriers, and interpreted the results from multiple lines of evidence and discussion. Physical performance analysis revealed that the paper used by the northern folk exhibits a lower apparent density, which is not conducive to the long-term preservation of paper. The preservation status investigation, curtain pattern analysis, and fiber analysis show that the paper used in the TFCD differs from traditional cultural paper regarding disease types, production precision, and fiber materials, providing a basis for its protection and restoration. The analysis of chemical components indicated that the aging and yellowing of paper can be correlated with the content of sulfur and carbonyl groups. The feasibility of using pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) analysis to quickly identify papermaking fibers in a large number of paper samples was proposed. By utilizing various techniques to inspect the paper of documents, this study helps to enhance the academic understanding of FCD materials. In addition, it expands the knowledge base of Northwest handmade paper.
Palm Leaf Manuscripts (PLMs) are commonly crafted from leaves of the talipot palm (Corypha umbraculifera) and the palmyra palm (Borassus flabellifer). To identify PLMs made from these two palm species, one chemical marker from the talipot palm and three from the palmyra palm are identified by application of Pyrolysis gas chromatography mass spectrometry (Py-GC/MS). These markers have successfully and been identified in recently manufactured PLMs as well as certain naturally aged PLMs, which indicates that they have specific identification values. The results of principal component analysis (PCA) on selected lignin pyrolysis products reveal a significant difference between the talipot palm and the three groups of the palmyra palm. For the identification of aged PLMs, a combination of the two analytical methods (Py-GC/MS and PCA) is necessary for accurate determination and discrimination of markers. This study provides a solid scientific foundation for determining the source plant species of ancient PLMs.
The use of birch tar has a long history, and its remains are found worldwide, especially in Europe, but few remains are found in Asia. Common characterization methods include gas chromatography/mass spectrometry (GC/MS), direct exposure electron ionization mass spectrometry (DE-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Py-GC/MS requires no solvent extraction, less sample than GC/MS, and no statistical analysis compared to DE-MS. However, Py-GC/MS has been rarely applied to identify birch tar because some critical characteristic molecules of birch tar were not identified. In this study, we first reported some biomarkers of birch tar that could be identified by Py-GC/MS in terms of analyzing modern birch tar. Then, the analysis criteria were used to analyze archaeological samples adhered to stone artifacts from a late Neolithic site (about 4000 BP) in northeast China. The results provide the earliest evidence of the exploitation of birch tar in northeast Asia up to date.
The occupation process and survival strategies of prehistoric humans on the Tibetan Plateau are important scientific questions for understanding human adaptation to extreme high-altitude environments. Here, we report a newly discovered microlithic site at Daiqu (DQ) in the Tongtian River basin of the central-eastern plateau. We collected 239 lithic artifacts from the DQ site for typological analysis. OSL and AMS 14 C dating samples were collected from the human active layer. Lipid residues from hearth sediments were analyzed, and we simulated and assessed environmental extremity and route accessibility for the site. Dating results suggest that the stable sedimentary layers began to form around 10.96 ± 0.56 ka BP at the DQ site. Human activity at DQ as early as 9271 ± 143 cal a BP, making it the earliest reported Holocene site with accurate stratigraphic dating on the plateau hinterland to date. Hearths and lithic artifacts indicate that the DQ site was a frequently used seasonal hunting camp, where quality lithic raw material was obtained and microliths processed. Prehistoric humans occupying the site relied on non-ruminant terrestrial animals as food resources. The DQ site is ideally situated to serve as a transit station for hunter-gatherers as they migrated between high and low elevations. Ameliorating Holocene climate promoted prehistoric human exploration of more environmentally extreme areas.