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The effect of heat on keratin and implications for the archaeological record

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Abstract

A horncore feature was encountered during excavations at Border Cave, in Member 2 BSL, dated 60–49 ka. The basal half of the horncore lay towards the centre of a combustion feature and was calcined. The tip half lay on a mat of burnt grass bedding towards the edge of the fireplace. It was covered with a black shiny residue, which was also present on nearby stone tools. The feature was jacketed and excavated later under a microscope in the laboratory. Raman spectroscopy identified the residue only as amorphous carbon, indicating the presence of a heated organic substance. Knowing that variation exists in modern and archaeological glue recipes, we wanted to know if the black residue was melted keratin, and if it was, whether it had been used as a substitute for beeswax or latex for hafting. We set out to test the hypothesis by conducting a heating experiment with a modern sheathed horncore. Experimental results showed that keratin does not transform into viable glue when heated. Instead, it reduces immediately to a glassy brittle residue. Our finding strongly supports a scenario of incidental deposition of residue on the archaeological stone tools. Previous combustion experiments have shown that the sediment below a fire can reach 300+ °C through vertical heat transfer. This implies that horn sheaths in archaeological deposits, separated from overlying combustion features by thousands of years, can transform into a black residue that may deposit on nearby stone and bone tools.

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Data availability

All relevant data are provided in the manuscript. Piece-plotted data taken using a total station theodolite are lodged with the curator of the Border Cave collection, Dr. Bernhard Zipfel, at the University of the Witwatersrand and with the South African Heritage Resource Agency (SAHRA). All finds are housed at the Evolutionary Studies Institute at the University of the Witwatersrand in Johannesburg, South Africa.

References

  • Aldeias V, Dibble HL, Sandgathe D, Goldberg P, McPherron SJP (2016) How heat alters underlying deposits and implications for archaeological fire features: a controlled experiment. J Archaeol Sci 67:64–79

    Article  Google Scholar 

  • Ambrose SH (1998) Chronology of the Later Stone Age and food production in East Africa. J Archaeol Sci 24:377–392

    Article  Google Scholar 

  • Backwell L, Wadley L, d’Errico F, Banks W, de la Peña P, Sievers C, Stratford D, Lennox S, Wojcieszak M, Bordy E, Bradfield J (2018) New excavations at Border Cave, KwaZulu-Natal, South Africa. J Field Archaeol 43(6):417–436

    Article  Google Scholar 

  • Binneman J, Mitchell PJ (1997) Usewear analysis of Robberg bladelets from Sehonghong Shelter, Lesotho. S Afr Field Archaeol 6:42–49

    Google Scholar 

  • Cahen D, Keeley LH (1980) Not less than 2, not more than 3. World Archaeol 12(2):166–180

    Article  Google Scholar 

  • Cahen D, Keeley LH, Vannoten FL (1979) Stone tools, toolkits, and human behavior in prehistory. Curr Anthropol 20(4):661–683

    Article  Google Scholar 

  • Cardamone JM (2010) Investigating the microstructure of keratin extracted from wool: peptide sequence (MALDI-TOF/TOF) and protein conformation (FTIR). J Mol Struct 969(1–3):97–105

    Article  Google Scholar 

  • Charrié-Duhaut A, Porraz G, Cartwright CR, Igreja M, Connan J, Poggenpoel C, Texier PJ (2013) First molecular identification of a hafting adhesive in the Late Howiesons Poort at Diepkloof Rock Shelter (Western Cape, South Africa). J Archaeol Sci 40:3506–3518

    Article  Google Scholar 

  • Cnuts D, Tomasso S, Rots V (2018) The role of fire in the life of an adhesive. J Archaeol Method Th 25(3):839–862

    Article  Google Scholar 

  • d’Errico F, Backwell LR, Villa P, Degano I, Lucejko J, Bamford M, Higham T, Colombini MP, Beaumont P (2012) Early evidence of San material culture represented by organic artifacts from Border Cave, South Africa. Proc Natl Acad Sci U S A 109(33):13214–13219

    Article  Google Scholar 

  • De Bie M, Caspar J-P (2000) Rekem. A Federmesser Camp on the Meuse River Bank. I.A.P. & Leuven University Press, Asse-Zellik and Leuven

    Google Scholar 

  • Deacon HJ, Deacon J (1980) The hafting, function and distribution of small convex scrapers with an example from Boomplaas Cave. S Afr Archaeol Bull 35:31–37

    Article  Google Scholar 

  • Edwards HGM, Newton EM, Russ J (2000) Raman spectroscopic analysis of pigments and substrata in prehistoric rock art. J Mol Struct 550-551:245–256

    Article  Google Scholar 

  • Gibson NE, Wadley L, Williamson BS (2004) Microscopic residues as evidence of hafting on backed tools from the 60000 to 68000 year-old Howiesons Poort layers of Rose Cottage Cave, South Africa. South Afr Humanit 16:1–11

    Google Scholar 

  • Koumouzelis M, Ginter B, Kozlowski JK, Pawlikowski M, Bar-Yosef O, Albert RM, Litynska-Zajac M, Stworzewicz E, Wojtal P, Lipecki G, Tomek T, Bochenski ZM, Pazdur A (2001) The early Upper Palaeolithic in Greece: the excavations in Klisoura Cave. J Archaeol Sci 28(5):515–539

    Article  Google Scholar 

  • Lombard M (2005) Evidence of hunting and hafting during the Middle Stone Age at Sibidu Cave, KwaZulu-Natal, South Africa: a multianalytical approach. J Hum Evol 48:279–300

    Article  Google Scholar 

  • Lombard M (2006) Direct evidence for the use of ochre in the hafting technology of Middle Stone Age tools from Sibudu Cave, KwaZulu-Natal. South Afr Humanit 18(1):57–67

    Google Scholar 

  • Lombard M (2007) The gripping nature of ochre: the association of ochre with Howiesons Poort adhesives and Later Stone Age mastics from South Africa. J Hum Evol 53:406–419

    Article  Google Scholar 

  • Maguregui M, Castro K, Morillas H, Trebolazabala J, Knuutinen U, Wiesinger R, Schreiner M, Madariaga JM (2014) Multianalytical approach to explain the darkening process of hematite pigment in paintings from ancient Pompeii after accelerated weathering experiments. Anal Methods-UK 6(2):372–378

    Article  Google Scholar 

  • Pétrequin P, Arbogast R-M, Bourquin-Mignot C, Lavier C, Viellet A (1998) Demographic growth, environmental changes and technical adaptations: responses of an agricultural community from the 32nd to the 30th centuries BC. World Archaeol 30(2):181–192

    Article  Google Scholar 

  • Phillipson DW (1976) The prehistory of eastern Zambia. British Institute in Eastern Africa

  • Pitarch A, Ruiz JF, Fdez-Ortiz de Vallejuelo S, Hernanz A, Maguregui M, Madariaga JM (2014) In situ characterization by Raman and X-ray fluorescence spectroscopy of post-Paleolithic blackish pictographs exposed to the open air in Los Chaparros shelter (Albalate del Arzobispo, Teruel, Spain). Anal Methods-UK 6(17):6641–6650

    Article  Google Scholar 

  • Prieto-Taboada N, Gómez-Laserna O, Martínez-Arkarazo I, Olazabal MÁ, Madariaga JM (2014) Raman spectra of the different phases in the CaSO4-H2O system. Anal Chem 86(20):10131–10137

    Article  Google Scholar 

  • Rots V, Van Peer P, Vermeersch PM (2011) Aspects of tool production, use, and hafting in Palaeolithic assemblages from Northeast Africa. J Hum Evol 60(5):637–664

    Article  Google Scholar 

  • Rots V, Lentfer C, Schmid VC, Porraz G, Conard NJ (2017) Pressure flaking to serrate bifacial points for the hunt during the MIS5 at Sibudu Cave (South Africa). PLoS One 12(4):e0175151

    Article  Google Scholar 

  • Sievers C, Wadley L (2008) Going underground: experimental carbonization of fruiting structures under hearths. J Archaeol Sci 35(11):2909–2917

    Article  Google Scholar 

  • Thackeray AI (2000) Middle Stone Age artefacts from the 1993 and 1995 excavations of Die Kelders Cave 1, South Africa. J Hum Evol 38:147–168

    Article  Google Scholar 

  • Tournié A, Prinsloo LC, Paris C, Colomban P, Smith B (2011) The first in situ Raman spectroscopic study of San rock art in South Africa: procedures and preliminary results. J Raman Spectrosc 42(3):399–406

    Article  Google Scholar 

  • Van Strydonck M, Boudin M, De Mulder G (2010) The carbon origin of structural carbonate in bone apatite of cremated bones. Radiocarbon 52(2):578–586

    Article  Google Scholar 

  • Villa P, Soriano S, Tsanova T, Higham T, d’Errico F, Backwell LR, Lucejko J, Beaumont P (2012) Border Cave and the beginning of the Later Stone Age in South Africa. Proc Natl Acad Sci U S A 109(33):13208–13213

    Article  Google Scholar 

  • Villa P, Pollarolo L, Degano I, Birolo L, Pasero M, Biagioni C, Douka K, Vinciguerra R, Lucejko JJ, Wadley L (2015) A milk and ochre paint mixture used 49,000 years ago in South Africa. PLoS One 10(6):e0131273

    Article  Google Scholar 

  • Wadley L (2010) Compound-adhesive manufacture as a behavioral proxy for complex cognition in the Middle Stone Age. Curr Anthropol 51(S1):S111–S119

    Article  Google Scholar 

  • Wadley L, Williamson BS, Lombard M (2004) Ochre in hafting in Middle Stone Age southern Africa: a practical role. Antiquity 78:661–675

    Article  Google Scholar 

  • Wadley L, Hodgskiss T, Grant M (2009) Implications for complex cognition from the hafting of tools with compound adhesives in the Middle Stone Age, South Africa. Proc Natl Acad Sci U S A 106:9590–9594

    Article  Google Scholar 

  • Wadley L, Trower G, Backwell L, d’Errico F (2015) Traditional glue, adhesive and poison used for composite weapons by Ju/‘hoan San in Nyae Nyae, Namibia. Implications for the evolution of hunting equipment in prehistory. PloS ONE 10(10)

  • Wadley L, Luong S, Sievers C, Prinsloo L (2019) Underground transfer of carbonised organic residues to lithics during preliminary fire experiments: implications for archaeology. Heritage Sci 7(1):59

    Article  Google Scholar 

  • Wendt WE (1976) ‘Art mobilier’ from the Apollo 11 Cave, South West Africa: Africa’s oldest dated works of art. S Afr Archaeol Bull 31:5–11

    Article  Google Scholar 

  • Werts SP, Jahren AH (2007) Estimation of temperatures beneath archaeological campfires using carbon stable isotope composition of soil organic matter. J Archaeol Sci 34(6):850–857

    Article  Google Scholar 

  • Williamson BS (2000) Prehistoric stone tool residue analysis from Rose Cottage Cave and other southern African sites. Ph.D. Thesis, University of the Witwatersrand

  • Williamson BS (2004) Middle Stone Age tool function from residue analysis at Sibudu Cave. S Afr J Sci 100:174–178

    Google Scholar 

  • Wojcieszak M (2018) Material processed with 58,000-year-old grindstones from Sibudu (KwaZulu-Natal, South Africa) identified by means of Raman microspectroscopy. J Raman Spectrosc 49:830–841

    Article  Google Scholar 

  • Wojcieszak MA, Wadley L (2018) Raman spectroscopy and scanning electron microscopy confirm ochre residues on 71 000-year-old bifacial tools from Sibudu, South Africa. Archaeometry 60(5):1062–1076

    Article  Google Scholar 

Download references

Acknowledgements

The Microscopy and Microanalysis Unit at the University of the Witwatersrand is thanked for the use of the Olympus BX63 microscope and the Raman spectrometer. We are grateful to Christine Steininger for identifying the archaeological and modern horns.

Funding

This research was funded by a National Geographic Explorer grant (NGS-54810R-19) and DSI-NRF Centre of Excellence in Palaeosciences grant (CEOOP2020-1) to LB.

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Lyn Wadley conceptualized the study and all the authors contributed to the design. Material preparation, data collection and analyses were performed by Lyn Wadley, Marine Wojcieszak and Lucinda Backwell. The first draft of the manuscript was written by Lucinda Backwell, and all the authors commented on previous versions of the manuscript. All the authors read and approved the final manuscript. Funding was acquired by Lucinda Backwell.

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Correspondence to Lucinda Backwell.

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Backwell, L., Wojcieszak, M. & Wadley, L. The effect of heat on keratin and implications for the archaeological record. Archaeol Anthropol Sci 12, 181 (2020). https://doi.org/10.1007/s12520-020-01152-9

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