Hostname: page-component-586b7cd67f-2plfb Total loading time: 0 Render date: 2024-11-25T07:48:09.788Z Has data issue: false hasContentIssue false
  • English
  • Français

Structural Characterization of Charcoal Exposed to High and Low Ph: Implications for 14C Sample Preparation and Charcoal Preservation

Published online by Cambridge University Press:  18 July 2016

N R Rebollo ,
I Cohen-Ofri ,
R Popovitz-Biro ,
O Bar-Yosef ,
L Meignen ,
P Goldberg ,
S Weiner  and
E Boaretto
N R Rebollo
Affiliation:
Radiocarbon Dating and Cosmogenic Isotopes Laboratory, Kimmel Center for Archaeological Science, Weizmann Institute of Science, Rehovot 76100, Israel
I Cohen-Ofri
Affiliation:
Department of Structural Biology, Weizmann Institute of Science, Rehovot 76100, Israel
R Popovitz-Biro
Affiliation:
Chemical Research Support Unit, Weizmann Institute of Science, Rehovot 76100, Israel
O Bar-Yosef
Affiliation:
Department of Anthropology, Peabody Museum, Harvard University, Cambridge 02138, Massachusetts, USA
L Meignen
Affiliation:
UNSA, CEPAM-CNRS, Sophia Antipolis, 06560 Valbonne, France
P Goldberg
Affiliation:
Department of Archaeology, Boston University, 675 Commonwealth Avenue, Boston 02215, Massachusetts, USA
S Weiner
Affiliation:
Department of Structural Biology, Weizmann Institute of Science, Rehovot 76100, Israel
E Boaretto*
Affiliation:
Radiocarbon Dating and Cosmogenic Isotopes Laboratory, Kimmel Center for Archaeological Science, Weizmann Institute of Science, Rehovot 76100, Israel Department of Land of Israel Studies and Archaeology, Bar-Ilan University, Ramat-Gan 52900, Israel
*
Corresponding author. Email: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Chemical and structural similarities between poorly preserved charcoal and its contaminants, as well as low radiocarbon concentrations in old samples, complicate 14C age determinations. Here, we characterize 4 fossil charcoal samples from the late Middle Paleolithic and early Upper Paleolithic strata of Kebara Cave, Israel, with respect to the structural and chemical changes that occur when they are subjected to the acid-base-acid (ABA) treatment. Differential thermal analysis and TEM show that acid treatment disrupts the structure, whereas alkali treatment results in the reformation of molecular aggregates. The major changes are ascribed to the formation of salt bridges at high pH and the disruption of the graphite-like crystallites at low pH. Weight losses during the treatments are consistently greater for older samples, implying that they are less well preserved. Based on the changes observed in vitro due to pH fluctuations, various methods for removing contamination, as well as a mechanism for preferential preservation of charcoal in nature, are proposed.

Type
Articles
Information
Radiocarbon , Volume 50 , Issue 2 , 2008 , pp. 289 - 307
Copyright
Copyright © 2008 by the Arizona Board of Regents on behalf of the University of Arizona 

References

Alon, D, Mintz, G, Cohen, I, Weiner, S, Boaretto, E. 2002. The use of Raman spectroscopy to monitor the removal of humic substances from charcoal: quality control for 14C dating of charcoal. Radiocarbon 44(1): 1–11.Google Scholar
Baruch, U, Werker, E, Bar-Yosef, O. 1992. Charred wood remains from Kebara Cave, Israel: preliminary results. Bulletin de la Société Botanique de France, Actualitiés Botaniques (2/3/4):531–8.Google Scholar
Bar-Yosef, O, Vandermeersch, B, Arensburg, B, Belfer-Cohen, A, Goldberg, P, Laville, H, Meignen, L, Rak, Y, Speth, JD, Tchernov, E, Tillier, A-M, Weiner, S. 1992. The excavations in Kebara Cave, Mt. Carmel. Current Anthropology 33(5):497–550.CrossRefGoogle Scholar
Bar-Yosef, O, Arnold, M, Mercier, N, Belfer-Cohen, A, Goldberg, P, Housley, R, Laville, H, Meignen, L, Vogel, JC, Vandermeersch, B. 1996. The dating of the Upper Paleolithic layers in Kebara Cave, Mt Carmel. Journal of Archaeological Science 23(2):297–306.CrossRefGoogle Scholar
Bird, MI, Ayliffe, LK, Fifield, LK, Turney, CSM, Cresswell, RG, Barrows, TT, David, B. 1999. Radiocarbon dating of “old” charcoal using a wet oxidation, stepped-combustion procedure. Radiocarbon 41(2):127–40.CrossRefGoogle Scholar
Bird, MI, Turney, CSM, Fifield, LK, Jones, R, Ayliffe, LK, Palmer, A, Cresswell, R, Robertson, S. 2002. Radiocarbon analysis of the early archaeological site of Nauwalabila I, Arnhem Land, Australia: implications for sample suitability and stratigraphic integrity. Quaternary Science Reviews 21(8–9):1061–75.Google Scholar
Chernysh, IG, Pakhovchishin, SV, Goncharik, VP. 1993. The activity of dispersed oxides on natural exfoliated graphite surfaces. Reaction Kinetic and Catalysis Letters 50(1–2):273–7.Google Scholar
Cohen-Ofri, I, Weiner, L, Boaretto, E, Mintz, G, Weiner, S. 2006. Modern and fossil charcoal: aspects of structure and diagenesis. Journal of Archaeological Science 33(3):428–39.Google Scholar
Cohen-Ofri, I, Popovitz-Biro, R, Weiner, S. 2007. Structural characterization of modern and fossilized charcoal produced in natural fires as determined by using electron energy loss spectroscopy. Chemistry: A European Journal 13(8):2306–10.Google ScholarPubMed
Dappe, YJ, Basanta, MA, Flores, F, Ortega, J. 2006. Weak chemical interaction and van der Waals forces between graphene layers: a combined density functional and intermolecular perturbation theory approach. Physical Review B 74: 205434-1–9.CrossRefGoogle Scholar
Franklin, RE. 1951. Crystallite growth in graphitizing and non-graphitizing carbons. Proceedings of the Royal Society of London A 209:196–218.Google Scholar
Frink, DS. 1992. The chemical variability of carbonized organic matter through time. Archaeology of Eastern North America 20:67–79.Google Scholar
Goldberg, P, Laville, H. 1991. Etude géologique de dépôts de la grotte de Kébara (Mont Carmel): campagnes 1982–1984. In: Bar-Yosef, O, Vandermeersch, B, editors. Le Squelette Mousterien de Kébara 2. Paris: Editions C.N.R.S. p 29–41. In French.Google Scholar
Kang, F, Leng, Y, Zang, T-Y, Li, B. 1998. Electrochemical synthesis and characterization of ferric chloride-graphite intercalation compounds in aqueous solution. Carbon 36(4):383–90.Google Scholar
Karkanas, P, Bar-Yosef, O, Goldberg, P, Weiner, S. 2000. Diagenesis in prehistoric caves: the use of minerals that form in situ to assess the completeness of the archaeological record. Journal of Archaeological Science 27(10):915–29.Google Scholar
Kucerík, J, Kovár, J, Pekar, M. 2004. Thermoanalytical investigation of lignite humic acids fractions. Journal of Thermal Analysis and Calorimetry 76(1):55–65.Google Scholar
Laville, H, Goldberg, P. 1989. The collapse of the Mousterian sedimentary regime and the beginning of the Upper Paleolithic at Debara. In: Bar-Yosef, O, Vandermeersch, B, editors. Investigations in South Levantine Prehistory. Oxford: BAR International Series 497. p 75–95.Google Scholar
Meignen, L, Goldberg, P, Bar-Yosef, O. 2008. The hearths at Kebara Cave and their role in site formation processes. In: Bar-Yosef, O, Meignen, L, editors. Kebara Cave, Mt. Carmel, Israel: The Middle and the Upper Paleolithic Archaeology. Part I. Cambridge, Massachusetts: Peabody Museum, Harvard University. p 91–122.Google Scholar
Moulijn, JA, Kapteijn, F. 1995. Towards a unified theory of reactions of carbon with oxygen-containing molecules. Carbon 33(8):1155–65.CrossRefGoogle Scholar
Olson, EA, Broecker, WS. 1958. Sample contamination and reliability of radiocarbon dates. Transactions of the New York Academy of Science Series II 20:593–604.CrossRefGoogle Scholar
Pietronero, L, Tosatti, E. 1981. Physics of Intercalation Compounds. Berlin: Springer-Verlag. 323 p.CrossRefGoogle Scholar
Rao, RB, Patnaik, N. 2004. Preparation of high pure graphite by alkali digestion method. Scandinavian Journal of Metallurgy 33(5):257–60.Google Scholar
Sakamoto, M, Kodaira, A, Imamura, M. 2004. An automated AAA preparation system for AMS radiocarbon dating. Nuclear Instruments and Methods in Physics Research B 223–224:298–301.CrossRefGoogle Scholar
Schiegl, S, Goldberg, P, Bar-Yosef, O, Weiner, S. 1996. Ash deposits in Hayonim and Kebara caves, Israel: macroscopic, microscopic and mineralogical observations, and their archaeological implications. Journal of Archaeological Science 23(5):763–81.Google Scholar
Schiffer, MB. 1986. Radiocarbon dating and the “old wood” problem: the case of Hohokam chronology. Journal of Archaeological Science 13(1):13–30.Google Scholar
Schlögl, R. 1987. Modification of the electronic structure of graphite by intercalation, chlorination and ion etching. Surface Science 189–190:861–72.Google Scholar
Shahack-Gross, R, Berna, F, Karkanas, P, Weiner, S. 2004. Bat guano and preservation of archaeological remains in cave sites. Journal of Archaeological Science 31(9):1259–72.CrossRefGoogle Scholar
Taylor, AW, Gurney, EL. 1961. Solubilities of potassium and ammonium taranakites. Journal of Physical Chemistry 65(9):1613–6.Google Scholar
Taylor, RE. 1987. Radiocarbon Dating: An Archaeological Perspective. Orlando: Academic Press. 212 p.Google Scholar
Trueman, CNG, Behrensmeyer, AK, Tuross, N, Weiner, S. 2004. Mineralogical and compositional changes in bones exposed on soil surfaces in Amboseli National Park, Kenya: diagenetic mechanisms and the role of sediment pore fluids. Journal of Archaeological Science 31(6):721–29.CrossRefGoogle Scholar
van der Waals, J. 1873. Over de Continuïteit van den Gas - en Vloeistoftoestand (On the continuity of the gas and liquid state) [PhD dissertation]. Leiden: Leiden University. In Dutch.Google Scholar
Wieber, AP, Guzman, JE, Wolf, EE. 2006. An STM study of phosphoric acid inhibition of the oxidation of HOPG and carbon catalyzed by alkali salts. Carbon 44(10):2069–79.Google Scholar
Yizhaq, M, Mintz, G, Cohen, I, Khalaily, H, Weiner, S, Boaretto, E. 2005. Quality controlled radiocarbon dating of bones and charcoal from the early Pre-Pottery Neolithic B (PPNB) of Motza (Israel). Radiocarbon 47(2):193–206.CrossRefGoogle Scholar