|Generate QR code
Open Access
Subscription Access
Raman Spectroscopy Analysis of Pigments from the Boyary I Rock Art Site, Khakassia
https://doi.org/10.17746/1563-0110.2025.53.2.054-062
Abstract
This article describes previously unknown paintings at the Boyary I rock art site, Republic of Khakassia. They are especially important because they were situated in the part of the panel where a missing ledge could have been located. The petroglyphs could indicate the time of its disappearance. Based on stylistic features, it is possible that they date to the Karasuk period (late 2nd to early 1st millennium BC). The article presents the results of Raman spectroscopy analysis of pigments detected in the paintings. The method involved their context assessment with regard to the rock surface and the white paint of recent inscriptions, the composition of ancient pigments, and searching for organic binder residue. The study covered panel 7 and the adjacent panels 8 and 9. The results are based on 103 spectra of various compositions. All three surfaces mainly consist of sandstone, the predominant constituents being albite, quartzite, and anatase, with occasional natural ferruginization. Modern white paint of two types—chalk (panel 7) and styrene acrylic (panel 9)—were detected. The red pigment used for the paintings in the right part of panel 7 consists of hematite. Calcium oxalate (whewellite) was found only where residues of pigments were located, suggesting that it resulted from the decomposition of the organic binder of the ancient paint.
Supporting agencies: This study was supported by the Russian Science Foundation, project No. 22-18-00070. The authors express their deep gratitude to E.V. Karpova, Senior Researcher at the Vorozhtsov Novosibirsk Institute of Organic Chemistry of the SB RAS, for her consultation, and thank the reviewer for constructive criticism which made it possible to significantly improve the text of the article. The study was carried out using scientific equipment of the Core Facilities Center “Cenozoic Geochronology” at the Institute of Archaeology and Ethnography of the SB RAS (Novosibirsk).
About the Authors
R. V. Davydov
Institute of Archaeology and Ethnography, Siberian Branch
Russian Federation
Russian Federation
Pr. Akademika Lavrentieva 17, Novosibirsk, 630090
Y. S. Gubar
Institute of Archaeology and Ethnography, Siberian Branch
Russian Federation
Russian Federation
Pr. Akademika Lavrentieva 17, Novosibirsk, 630090
L. V. Zotkina
Institute of Archaeology and Ethnography, Siberian Branch
Russian Federation
Russian Federation
Pr. Akademika Lavrentieva 17, Novosibirsk, 630090
References
1. Berlanga G., Acosta-Maeda T.E., Sharma S.K., Porter J.N., Dera P., Shelton H., Taylor G.J., Misra A.K. 2019 Remote Raman spectroscopy of natural rocks. Applied Optics, vol. 58 (32), Art. No. 8971.
2. Bonneau A., Pearce D.G., Pollard A.M. 2012 A multi-technique characterization and provenance study of the pigments used in San rock art, South Africa. Journal of Archaeological Science, vol. 39 (2): 287–294.
3. Donnely F.C., Purcell-Milton F., Framont V., Cleary O., Dunne P.W., Gun’ko Y.K. 2017 Synthesis of CaCO3 nano- and micro-particles by dry ice carbonation. Chemical Communications, vol. 53 (49): 6657–6660.
4. Esin Y.N., Magai Z., Ruselier E., Walter F. 2014 Kraska v naskalnom iskusstve okunevskoy kultury Minusinskoy kotloviny. Rossiyskaya arkheologiya, No. 3: 79–89.
5. Fido L.A., Bell S.E.J. 2006 Raman spectroscopy for rapid analysis of white household paints. Advertising Supplement, No. 1: 1–4.
6. Freeman J.J., Wang A., Kuebler K.E., Jolliff B.L., Haskin L.A. 2008 Characterization of natural feldspars by Raman spectroscopy for future planetary exploration. The Canadian Mineralogist, vol. 46 (6): 1477–1500.
7. Fremont W., Verboven M., Saverwyns S. 2014 Accelerated tobacco smoke staining on waterborne acrylic paintings caused by exuding surfactants: a study with py-GC/MS and THM-GC/MS. e-Preservation Science, No. 4: 47–53.
8. Froment F., Tournie A., Colomban P. 2008 Raman identifi cation of natural red to yellow pigments: ochre and iron containing ores. Journal of Raman Spectroscopy, vol. 39 (5): 560–568.
9. Gryaznov M.P. 1971 Miniatyury tashtykskoy kultury: Iz rabot Krasnoyarskoy ekspeditsii 1968 g. In Arkheologicheskiy sbornik. Iss. 13: Materialy i issledovaniya po arkheologii SSSR. Leningrad: Avrora, pp. 94–106.
10. Gunn R.G., Douglas L.C., Whear R.L. 2014 Interpreting’ polychrome paintings using DStretch. Rock Art Research, vol. 31 (1): 1–4.
11. Hernanz A. 2015 Raman spectroscopy of prehistoric pictorial materials. In Prehistoric Art as Prehistoric Culture, P. Bueno Ramírez, P.G. Bahn (eds.). Oxford: Archaeopress, pp. 11–19.
12. Hernanz A., Gavira-Vallejo J.M., Ruiz-López J.F. 2006 Introduction to Raman microscopy of prehistoric rock paintings from the Sierra de las Cuerdas, Cuenca, Spain. Journal of Raman Spectroscopy, vol. 37 (10): 1054–1062.
13. Iriarte M., Hernanz A., Ruiz-López J.F., Martín S. 2013 μ-Raman spectroscopy of prehistoric paintings from the Abrigo Remacha rock shelter (Villaseca, Segovia, Spain). Journal of Raman Spectroscopy, vol. 44 (11): 1557–1562.
14. Kovaleva O.V. 2011 Naskalniye risunki epokhi pozdney bronzy Minusinskoy kotloviny. Novosibirsk: Izd. IAET SO RAN.
15. Kovtun I.V. 2001 Izobrazitelniye traditsii epokhi bronzy Tsentralnoy i Severo-Zapadnoy Azii: Problemy genezisa i khronologii ikonografi cheskikh kompleksov severo-zapadnogo SayanoAltaya. Novosibirsk: Izd. IAET SO RAN.
16. Leontiev N.V., Bokovenko N.A. 1985 Kavkazskaya pisanitsa na Tube. KSIA. Iss. 184: Zhelezniy vek Kavkaza, Sredney Azii i Sibiri: 82–88.
17. Leontiev N.V., Kapelko V.F., Esin Y.N. 2006 Izvayaniya i stely okunevskoy kultury. Abakan: Khakas. kn. izd.
18. Lofrumento C., Ricci M., Bachechi L., De Feo D., Castellucci E.M. 2012 The first spectroscopic analysis of Ethiopian prehistoric rock painting. Journal of Raman Spectroscopy, vol. 43 (6): 809–816.
19. Maksimenkov G.A. 1980 Mogilnik Chernovaya VIII – etalonniy pamyatnik okunevskoy kultury. In Pamyatniki okunevskoy kultury. Leningrad: Nauka, pp. 3–26.
20. Morozov Y.A., Smulskaya A.I., Kulakovskiy A.L., Matveev M.A. 2019 Strukturno-veshchestvenniye preobrazovaniya krasnotsvetnogo peschanika v seismogennom zerkale skolzheniya. Trudy Fersmanovskoy nauchnoy sessii GI KNC RAN, No. 16: 388–392.
21. Noda L.K., Sala O. 2000 Resonance Raman investigation on the interaction of styrene and 4-methyl styrene oligomers on sulphated titanium oxide. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, vol. 56 (1): 145–155.
22. Pakhunov A.S., Zhitenev V.S., Brandt N.N., Chikishev A.Y. 2014 Predvaritelniye rezultaty kompleksnogo issledovaniya krasochnykh pigmentov nastennykh izobrazheniy Kapovoy peshchery. Vestnik arkheologii, antropologii i etnografii, No. 4: 4–15.
23. Polyakov A.V. 2022 Khronologiya i kulturogenez pamyatnikov epokhi paleometalla Minusinskikh kotlovin. St. Petersburg: Izd. IIMK RAN.
24. Rousaki A., Vázquez C., Aldazábal V., Bellelli C., Calatayud M.C., Hajduk A., Vargas E., Palacios O., Vandenabeele P., Moens L. 2017 The first use of portable Raman instrumentation for the in situ study of prehistoric rock paintings in Patagonian sites. Journal of Raman Spectroscopy, vol. 48 (11): 1–9.
25. Ruiz J.F., Hernanz A., Armitage R.A., Rowe M.W., Viñas R., Gavira-Vallejo J.M., Rubio A. 2012 Calcium oxalate AMS 14C dating and chronology of postPalaeolithic rock paintings in the Iberian Peninsula. Two dates from Abrigo de los Oculados (Henarejos, Cuenca, Spain). Journal of Archaeological Science, vol. 39 (8): 2655–2667.
26. Rusakova I.D. 2001 Petroglificheskiy kompleks “Boyary – AbakanoPerevoz” v Khakasii i yego mesto v prirodno-istoricheskom landshafte. Cand. Sc. (History) Dissertation. Kemerovo.
27. Sher Y.A. 1980 Petroglify Sredney i Tsentralnoy Azii. St. Petersburg: Nauka.
28. Silaev V.I., Lyutoev V.P., Petrovskiy V.A., Khazov A.F. 2013 Opyt issledovaniy prirodnykh uglerodistykh veshchestv i nekotorykh ikh sinteticheskikh analogov metodom ramanovskoy spektroskopii. Mineralogicheskiy zhurnal, vol. 35 (3): 33–47.
29. Smith D.C., Bouchard M., Lorblanchet M. 1999 An initial Raman microscopic investigation of prehistoric rock art in caves of the Quercy District, SW France. Journal of Raman Spectroscopy, vol. 30 (4): 347–354.
30. Vadetskaya E.B. 1980 Izvayaniya okunevskoy kultury. In Pamyatniki okunevskoy kultury. Leningrad: Nauka, pp. 37–87.
31. Vadetskaya E.B. 1986 Arkheologicheskiye pamyatniki v stepyakh Srednego Yeniseya. Leningrad: Nauka.
32. Wiesinger R., Pagnin L., Anghelone M., Moretto L.M., Orcega E.F., Schreiner M. 2018 Pigment and binder concentrations in modern paint samples determined by IR and Raman spectroscopy. Angewandte Chemie International Edition, vol. 57 (25): 1–8.
33. Wojcieszak M., Wadley L.A. 2019 Raman micro-spectroscopy study of 77,000 to 71,000-year-old ochre processing tools from Sibudu, KwaZulu-Natal, South Africa. Heritage Science, vol. 7 (1), Art. No. 24.
34. Zotkina L.V., Sutugin S.V. 2023 Possibilities of direct dating of rock art in the KhakassMinusinsk basin. Archaeology, Ethnology and Anthropology of Eurasia, vol. 51 (1): 59–69. (In Russian and English).
35. Zotkina L.V., Sutugin S.V., Postnikov N.V., Rusakova I.D., Davydov R.V. 2021 Naskalnoye iskusstvo rannego plasta na territorii Minusinskoy kotloviny: Opyt sistematizatsii dannykh i eksperimentalno-trasologicheskogo issledovaniya. In Problemy arkheologii, etnografi i i antropologii Sibiri i sopredelnykh territoriy, vol. XXVII. Novosibirsk: Izd. IAET SO RAN, pp. 453–458.
Review
For citations:
Davydov R.V., Gubar Y.S., Zotkina L.V. Raman Spectroscopy Analysis of Pigments from the Boyary I Rock Art Site, Khakassia. Archaeology, Ethnology & Anthropology of Eurasia. 2025;53(1):54-62. https://doi.org/10.17746/1563-0110.2025.53.2.054-062
Views:
0
Email this article 