The forgotten framework: analysis of organic residues on Bronze Harness Ornaments of Shang and Western Zhou Dynasties unearthed at Xitou site in Shaanxi, China
Source abstract
Abstract
To examine the form of harnesses from the Shang and Western Zhou dynasties (16th–8th century B.C.) in China, this study analyzed the black-brown granular and thin-striped organic residues found on the bronze 韅 (Xian, a leather belt around a horse’s abdomen) ornaments unearthed from the Shangmiao Cemetery of Xitou Site in Xunyi (Shaanxi, China). The residues were investigated by microscope, scanning electron microscopy (SEM), Raman spectroscopy (Raman), Fourier transform infrared spectroscopy (FTIR), and Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS). The results revealed that the microstructure of the residues closely resembled leather relics, and infrared analysis indicated that the residues contained proteins, confirming their identification as leather. Further analysis by ZooMS (Zooarchaeology by Mass Spectrometry) confirmed the leather to be Bovini ( Bos ) hide. This suggests that the use of Bovini hide as a material for making Xian was well established during the Shang and Zhou periods. The leather likely served to connect the various parts of the harness and fasten it to the horse for use. This study marks the first research of Xian from these periods in China. The residues have survived attributed to the bactericidal effect of copper ions on the surface of the bronze Xian ornaments and the potential mineralization of the leather. Additionally, peculiar curly green bundles found within the residues are hypothesized to be related to the formation of copper soap or curly malachite.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Cultural Heritage Materials Analysis · Archaeology and ancient environmental studies · Pacific and Southeast Asian Studies
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (60)
Show source-provided references
1. Outram, A. K. et al. The earliest horse harnessing and milking. Science. 323, 1332–1335 (2009).10.1126/science.1168594 ↗
2. Wu, X. Y. Study on chariot burials in early China, 1200-221 BCE. 1–2 (Chinese Science Press, Beijing, 2009).
3. Xun, K. Xunzi. 301 (Zhonghua Book Company, Beijing, 2011).
4. Liu, Y. H. Ancient Chinese Carriages and Horses. 120 (Tsinghua University Press, Beijing, 2013).
5. Wang, Y., Zhong, J. R. & Lei, X. S. New insight into the bronze plaque-shaped ornaments of Xian of the Western Zhou Dynasty. Cult Relics. 3, 64–76 (2023).
6. Yang, H. The development and external influence of ancient Chinese harnesses. Cult Relics. 9, 45–54 (1984).
7. Dong, G. A comparative study on the horse fittings of Murong Xianbei, Gaogouli, Korea and Japan. Cult Relics. 10, 34–42 (1995).
8. Rawson, J., Huan, L. & Taylor, W. T. T. Seeking horses: allies, clients and exchanges in the Zhou Period (1045–221 BC). J World Prehist. 34, 489–530 (2021).10.1007/s10963-021-09161-9 ↗
9. p, Wang, Mei, J. J. & Zhang, Y. Z. Scientific analysis of the bronzes from Shimenzi cemetery, Hutubi county, Xinjiang. The Western Regions Stud. 4, 44–55 (2014).
10. Liu, Y. et al. China and the steppe: technological study of precious metalwork from Xigoupan Tomb 2 (4th–3rd c. BCE) in the Ordos region, Inner Mongolia. Herit Sci. 9, 46 (2021).10.1186/s40494-021-00520-5 ↗
11. Wang, H. T. & Zhang, H. Y. Study on the conservation and restoration of two misplaced gold and silver iron harnesses unearthed from the Han tomb of Luozhuang, Jinan, Shandong, China. Southern Herit. 2, 283–289 (2019).
12. Wang, D., Wang, H. M. & Liu, Y. Rope-shaped Horse Tack Unearthed from Miaoshanjian site in Quzhou of Zhejiang Province. Jiang Han Archaeol. 3, 115–120 (2022).
13. Li, Y. H. et al. Scientific study of organic residues attached to a harness unearthed from Shangmiao site in Xunyi County. Sci. Conserv. Archaeol. 35, 46–51 (2023).
14. Wertmann, P. et al. The earliest directly dated saddle for horse-riding from a mid-1st millennium BCE female burial in Northwest China. Archaeolo Res. Asia. 35, 100451 (2023).10.1016/j.ara.2023.100451 ↗
15. Gu, F. Study on the carriage and horse burials unearthed at the Qianzhada Cemetery in Tengzhou, Shandong Province. Three Dynasties Archaeol. 00, 483–502 (2006).
16. Hubei Provincial Institute of Cultural Relics and Archaeology, Jingmen Museum, Archaeological Team of Xiang-Jing Expressway. Zuozhong Chu Tombs in Jingmen. Beijing: Cultural Relics Press; 2006. p. 118.
17. Chen, Z. L., Wu, Y. L. & Sun, S. Y. Application of light microscope technique in leather research. West Leather. 11, 41–43 (2010).
18. Zhang, Y. et al. Identification of waterlogged leather unearthed from a Warring States Period tomb in Yiyuan, Shandong Province. Sci. Conserv. Archaeol. 27, 59–64 (2015).
19. Mirghani, M. E. S. et al. Rapid authentication of leather and leather products. Adv. Nat. Appl. Sci. 6, 651–660 (2012).
20. Falcao, L. & Araujo, M. E. M. Application of ATR–FTIR spectroscopy to the analysis of tannins in historic leathers: the case study of the upholstery from the 19th century Portuguese Royal Train. Vib Spectrosc. 74, 98–103 (2014).10.1016/j.vibspec.2014.08.001 ↗
21. Zhang, X. & Lange, S. Leather species identification via mitochondrial DNA polymerase chain reaction. J. Am. Leather Chem. Assoc. 114, 265–270 (2019).
22. Merheb, M. et al. DNA for species identification in leather: fraud detection and endangered species protection. Res. J. Biotechnol. 10, 65–68 (2015).
23. Schröder, O. et al. Ancient DNA identification of domestic animals used for leather objects in Central Asia during the Bronze Age. Holocene 26, 1722–1729 (2016).10.1177/0959683616641741 ↗
24. Pothier Bouchard, G. A ZooMS-informed archaeozoological and taphonomic analysis comparing Neanderthal and Homo sapiens subsistence behaviours in Northwest Italy. Université de Montréal. 46 (2022).
25. Ge, R. C. et al. Multi-faceted analysis reveals the characteristics of silk fabrics on a Liao Dynasty DieXie belt. Herit Sci. 11, 217 (2023).10.1186/s40494-023-01064-6 ↗
26. Liu, L. et al. ZooMS identification of the origin of painted protein-based adhesive of clay sculptures from the Astana cemetery. Collect. Stud. Archaeol. 01, 707–716 (2022).
27. Buckley, M. et al. Distinguishing between archaeological sheep and goat bones using a single collagen peptide. J. Archaeol. Sci. 37, 13–20 (2010).10.1016/j.jas.2009.08.020 ↗
28. Wei, X. X. et al. Brief report on the survey of Xitou Site in Xunyi County, Shaanxi Province. Steppe Cult Relics. 1, 16–27 (2020).
29. Fairbank, J. K. & Feuerwerker, A. The Cambridge history of ancient China: from the origins of civilization to 221 BC. 292 (Cambridge University Press, 1999).
30. Sima Q. Records of the Historian. 112–114 (Zhonghua Book Company, Beijing, 1963).
31. Welker, F. et al. Ancient proteins resolve the evolutionary history of Darwin’s South American ungulates. Nature. 522, 81–84 (2015).10.1038/nature14249 ↗
32. Niedermeyer, T. H. J. & Strohalm, M. mMass as a software tool for the annotation of cyclic peptide tandem mass spectra. Plos ONE. 7, e44913 (2012).10.1371/journal.pone.0044913 ↗
33. Scott, D. A. An examination of the patina and corrosion morphology of some Roman bronzes. J. Am. Inst. Conserv. 33, 1–23 (1994).10.1179/019713694806066419 ↗
34. Jakes, K. A. & Howard III, J. H. Replacement of protein and cellulosic fibers by copper minerals and the formation of textile pseudomorphs. In (eds Howard L. Needles, S. Haig Zeronian) Historic Textile and Paper Materials (Washington DC: ACS Publications, 1984).
35. Yang, J. Mold identification and remediation of cultural relics based on scanning electron microscopy. J. Chin. Electron Microsc. Soc. 39, 65–70 (2020).
36. Vyskočilová, G. et al. Burial-induced deterioration in leather: a FTIR-ATR, DSC, TG/DTG, MHT and SEM study. Herit Sci. 10, 7 (2022).10.1186/s40494-021-00638-6 ↗
37. Zhang, X. L. et al. Research on leather artifacts from Inner Mongolia: classification, composition and analysis of the properties related to the technology of manufacture. Sci. Conserv. Archaeol. 24, 33–44 (2012).
38. Hu, Y. et al. Artificial deterioration of vegetable-tanned leather under synergistic effect of temperature and humidity. J. Cult Herit. 53, 118–126 (2022).10.1016/j.culher.2021.11.007 ↗
39. Chen, Q. et al. Influences of high temperature and humidity on vegetable-tanned leather. J. Cult. Herit. 68, 375–387 (2024).10.1016/j.culher.2024.07.001 ↗
40. Coccato, A. et al. Raman spectroscopy of green minerals and reaction products with an application in Cultural Heritage research. J. Raman Spectrosc. 47, 1429–1443 (2016).10.1002/jrs.4956 ↗
41. Wei, G. F. et al. A preliminary study on the difference between natural oxide copper ore and corrosion product of the bronze ware. Sci. Conserv. Archaeol. 17, 9–14 (2005).
42. Welker, F. et al. Using ZooMS to identify fragmentary bone from the late Middle/Early Upper Palaeolithic sequence of Les Cottés, France. J. Archaeol. Sci. 54, 279–286 (2015).10.1016/j.jas.2014.12.010 ↗
43. Li, Y. et al. A study of the Pre-Zhou subsistence economy in the ancient Bin area using faunal remains from the Site of Zaolinhetan in Xunyi, Shaanxi Province. Agricult. Hist Chin. 38, 33–42 (2019).
44. Hua J. M. Chinese Handicraft. 104 (Elephant Press, Zhengzhou, 2014).
45. Borkow, G. & Gabbay, J. Copper as a biocidal tool. Curr. Med. Chem. 12, 2163–2175 (2005).10.2174/0929867054637617 ↗
46. Chen, H. L., Jakes, K. A. & Foreman, D. W. SEM, EDS, and FTIR examination of archaeological mineralized plant fibers. Text Res. J. 66, 219–224 (1996).10.1177/004051759606600406 ↗
47. Davis, M. & Harris, S. Textiles in a Viking Age hoard: identifying ephemeral traces of textiles in metal corrosion products. J. Archaeol. Sci. Rep. 48, 103796 (2023).
48. Carvalho, L. D. C. et al. Unlocking the organic residues preserved in the corrosion from the Pewsey Hoard vessels. Sci. Rep. 12, 21284 (2022).10.1038/s41598-022-24400-5 ↗
49. Carvalho, L. D. C. et al. Investigating the organic residues from the corrosion of a caccabus from Pompeii. J. Archaeol. Sci. Rep. 46, 103638 (2022).
50. Iacconi, C. et al. Virtual technical analysis of archaeological textiles by synchrotron microtomography. J. Archaeol. Sci. 149, 105686 (2023).10.1016/j.jas.2022.105686 ↗
51. Jakes, K. A. & Sibley, L. R. An examination of the phenomenon of textile fabric pseudomorphism. Adv. Chem. Ser. 205, 403–424 (1984).10.1021/ba-1984-0205.ch020 ↗
52. Scott D. A. Copper and Bronze in art: Corrosion, Colorants, Conservation (Los Angeles: Getty publications, 2002).
53. Guthrie, R. E. & Laurie, S. H. The binding of copper (II) to mohair keratin. Aus. J. Chem. 21, 2437–2443 (1968).10.1071/CH9682437 ↗
54. da Costa Carvalho, L. Beyond Copper Soaps: characterization of copper corrosion containing organics (Gewerbestrasse: Springer Nature, 2022).10.1007/978-3-030-97892-1 ↗
55. Nevin, A. et al. The identification of copper oxalates in a 16th century Cypriot exterior wall painting using micro FTIR, micro Raman spectroscopy and Gas Chromatography-Mass Spectrometry. J. Cult. Herit. 9, 154–161 (2008).10.1016/j.culher.2007.10.002 ↗
56. Eggert, G. Pseudomorph or corrosion? The enigma of the curly malachite. Metal 7, 57–60 (2007).
57. Eggert, G. Copper and Bronze in Art’ and the Search for Rare Corrosion Products. Heritage. 6, 1768–1784 (2023).10.3390/heritage6020094 ↗
58. Nienhuis, J. et al. Curly malachite on archaeological bronze: a systematic study of the shape and phenomenological approach of its formation mechanism. e-Preservation Sci. 13, 23–32 (2016).
59. Lieber, W. Locken. Ringe und Spiralen-kuriose Wachstumsformen von Kristallen. Der. Aufschluss. 55, 3–16 (2004).
60. Werner, U. et al. The removal of metal soaps from brass beads on a leather belt. Stud. Conserv. 57, 3–20 (2012).10.1179/2047058411Y.0000000004 ↗