Skip to main content
SpringerLink
Log in

Combining TXRF, FT-IR and GC–MS information for identification of inorganic and organic components in black pigments of rock art from Alero Hornillos 2 (Jujuy, Argentina)

  • Original Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Archaeological samples are complex in composition since they generally comprise a mixture of materials submitted to deterioration factors largely dependent on the environmental conditions. Therefore, the integration of analytical tools such as TXRF, FT-IR and GC–MS can maximize the amount of information provided by the sample. Recently, two black rock art samples of camelid figures at Alero Hornillos 2, an archaeological site located near the town of Susques (Jujuy Province, Argentina), were investigated. TXRF, selected for inorganic information, showed the presence of manganese and iron among other elements, consistent with an iron and manganese oxide as the black pigment. Aiming at the detection of any residual organic compounds, the samples were extracted with a chloroform–methanol mixture and the extracts were analyzed by FT-IR, showing the presence of bands attributable to lipids. Analysis by GC–MS of the carboxylic acid methyl esters prepared from the sample extracts, indicated that the main organic constituents were saturated (C16:0 and C18:0) fatty acids in relative abundance characteristic of degraded animal fat. The presence of minor C15:0 and C17:0 fatty acids and branched-chain iso-C16:0 pointed to a ruminant animal source.

Rock art painting at Hornillos 2 Cave, Susques, Argentina

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Chalmin E, Menu M, Vignaud C (2003) Meas Sci Technol 14:1590–1597

    Article  CAS  Google Scholar 

  2. Garate D, Laval E, Menu M (2004) Lánthropologie 108:251–289

    Article  Google Scholar 

  3. Scott DA, Hyder WD (1993) Studin Conserv 38:155–173

    Article  CAS  Google Scholar 

  4. Loy TH, Jones R, Nelson DE, Mehan B, Vogel J, Southon J, Cosgrove R (1990) Antiquity 64:110–116

    Google Scholar 

  5. Nelson DE, Chaloupka G, Chippindale C, Alderson MS, Southon JR (1995) Archaeometry 37:151–156

    Article  CAS  Google Scholar 

  6. Watchman A, Cole N (1993) Antiquity 67:355–358

    Google Scholar 

  7. Spades S, Russ J (2005) Archaeometry 47:115–126

    Article  CAS  Google Scholar 

  8. Aschero CA (1983-85) Cuad Inst Nac Antropol 10:291–306

    Google Scholar 

  9. Aschero CA, Podestá MM (1986) Runa XVI:29–57

    Google Scholar 

  10. Boschín MT, Seldes AM, Maier MS, Casamiquela RM, Ledesma R, Abad G (2002) Zephyrus 55:183–198

    Google Scholar 

  11. Vázquez C (2007) Report IAEA/AL/181:29–34

  12. Vázquez C, Maury AM, Albornoz A, Hajduk A. (2006) Brazilian Synchrotron Light Laboratory, Activity report. In press

  13. Maier MS, de Faria DLA, Boschín MT, Parera SD, del Castillo Bernal MF (2007) Vib Spectrosc 44:182–186

    Article  CAS  Google Scholar 

  14. Rial GE, Barbosa CE (1983–85) Cuad Inst Nac Antropol 10:313–317

    Google Scholar 

  15. Wainwright INM, Helwig K, Rolandi DS, Gradin C, Podestá MM, Onetto M, Aschero CA (2002) Rock paintings conservation and pigment analysis at Cueva de las Manos and Cerro de los Indios, Santa Cruz (Patagonia), Argentina. In: Vontobel R (ed) 13th Triennial Meeting Rio de Janeiro, vol 2. James and James, London

    Google Scholar 

  16. Wainwright INM, Helwig K, Podestá MM, Belelli C (2000) Analysis of pigments from rock painting sites in Rio Negro and Chubut Provinces. In: Podestá MM, de Hoyos M (eds) Arte en las rocas. Arte rupestre, menhires y piedras de colores en la Argentina Sociedad Argentina de Antropología y Asociación de Amigos del Instituto Nacional de Antropología y Pensamiento Latinoamericano, Buenos Aires

  17. Parera SD, Maier MS, Llamazares AM (2007) Identificación de 5-metoxi-N,N-dimetiltriptamina en pinturas rupestres de la provincia de Catamarca. In Rosa Erra Balsells (ed.) XVI Simposio Nacional de Química Orgánica (Sociedad Argentina de Investigación en Química Orgánica), Buenos Aires

  18. Yacobaccio HD, Catá MP, Morales MR, Joly D, Azcune C (2007) Ocupaciones humanas tempranas en la Puna de Atacama: el Alero Hornillos 2, Susques (Jujuy). British Archaeological Reports (in press)

  19. von Bohlen A (2004) e-Preservationscience 1:23–34

    Google Scholar 

  20. Pepe C, Clottes J, Menu M, Walter PH (1991) Acad Sci Paris 312:929–934

    Google Scholar 

  21. Regert M, Garnier N, Decavallas O, Cren-Olivé C, Rolando C (2003) Meas Sci Technol 14:1620–1630

    Article  CAS  Google Scholar 

  22. Munsell Soil Colour Charts (1994) Macbeth, New York

  23. Guineau B, Lorblanchet M, Gratuze B, Dulin L, Roger P, Akrich R, Muller F (2001) Archaeometry 43:211–225

    Article  CAS  Google Scholar 

  24. Hradil H, Grygar T, Hradilová J, Bezdicka P (2003) Appl Clay Sci 22:223–36

    Article  CAS  Google Scholar 

  25. Helwig K (2007) Iron oxide pigments. Natural and synthetic. In: Berrie BH (ed) Artists’ pigments. A handbook of their history and characteristics vol 4. Archetype, London

    Google Scholar 

  26. Nullo FE (1988) Descripción geológica de la Hoja 4 a-b Susques, Provincia de Jujuy. SEGEMAR Argentina

  27. Turner JC, Méndez V (1979) Puna. Geología Regional Argentina. Volumen I. Academia Nacional de Ciencias, Córdoba

    Google Scholar 

  28. Coira BL (1999) Recursos Minerales de la República Argentina, SEGEMAR, Anales 35:1557–1567. Buenos Aires

  29. Derrick MR, Stulik D, Landry JM (1999) Infrared spectroscopy in conservation science. The Getty Conservation Institute, Los Angeles

    Google Scholar 

  30. Spangenberg JE, Jacomet S, Schibler J (2006) J Archaeol Sci 33:1–13

    Article  Google Scholar 

  31. Copley MS, Bland HA, Rose P, Horton M, Evershed RP (2005) Analyst 130:860–871

    Article  CAS  Google Scholar 

  32. Kimpe K, Jacobs PA, Waelkens M (2001) J Chromatogr A 937:87–95

    Article  CAS  Google Scholar 

  33. Kimpe K, Jacobs PA, Waelkens M (2002) J Chromatogr A 968:151–160

    Article  CAS  Google Scholar 

  34. Mirabaud S, Rolando C, Regert M (2007) Anal Chem 79:6182–6192

    Article  CAS  Google Scholar 

  35. Zhou Y, Sheng G, Fu J, Geng A, Chen J, Xiong Y, Zhang Q (2003) Chem Geol 199:343–359

    Article  CAS  Google Scholar 

  36. Wendt CJ, Lu S-T (2006) J. Archaeol Sci 33:89–97

    Article  Google Scholar 

  37. Maurer J, Möhring T, Rullkötter J (2002) J. Archaeol Sci 29:751–762

    Article  Google Scholar 

  38. Bothe CI (2007) Asphalt. In: Berrie BH (ed) Artists’ pigments. A handbook of their history and characteristics, vol 4. Archetype, London

    Google Scholar 

  39. Alonso RN (2006) Ser Correl Geol 21:155–170

    Google Scholar 

Download references

Acknowledgements

This research was supported by the University of Buenos Aires (Grant X314) and IAEA (contract no. 13864). M.S.M., P.S., and H.Y. are Research Members of the National Research Council of Argentina (CONICET). We thank Graciela Custo and Martha Ortiz, María Susana Alonso, and Mariana Rosenbusch for TXRF, XRD and SEM-EDX analyses, respectively.

Author information

Authors and Affiliations

  1. Chemistry Department, Comisión Nacional de Energía Atómica, Av. Gral Paz 1499, (B1650KNA), Buenos Aires, Argentina

    Cristina Vázquez

  2. Facultad de Ingeniería, Universidad de Buenos Aires, Av. Paseo Colón 1650 (C1063ACV), Buenos Aires, Argentina

    Cristina Vázquez

  3. UMYMFOR and Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, (C1428EGA), Buenos Aires, Argentina

    Marta S. Maier & Sara D. Parera

  4. Instituto de Arqueología, Universidad de Buenos Aires, 25 de Mayo 221 - 3° Piso (C1002ABE), Buenos Aires, Argentina

    Hugo Yacobaccio & Patricia Solá

Authors
  1. Cristina Vázquez
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Marta S. Maier
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sara D. Parera
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hugo Yacobaccio
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Patricia Solá
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Cristina Vázquez.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Vázquez, C., Maier, M.S., Parera, S.D. et al. Combining TXRF, FT-IR and GC–MS information for identification of inorganic and organic components in black pigments of rock art from Alero Hornillos 2 (Jujuy, Argentina). Anal Bioanal Chem 391, 1381–1387 (2008). https://doi.org/10.1007/s00216-008-2038-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-008-2038-4

Keywords

Search

Navigation