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

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.Anthropolog

Alkali extraction of archaeological and geological charcoal: evidence for diagenetic degradation and formation of humic acids

Charcoal forms a crucial source of archaeological and palaeoenvironmental data, providing a record of cultural activities, past climatic conditions and a means of chronological control via radiocarbon (<sup>14</sup>C) dating. Key to this is the perceived resistance of charcoal to post-depositional alteration, however recent research has highlighted the possibility for alteration and degradation of charcoal in the environment. An important aspect of such diagenesis is the potential for addition of exogenous 'humic acids' (HAs), to affect the accuracy of archaeological and palaeoenvironmental reconstructions based upon chemical analyses of HA-containing charcoal. However the release of significant quantities of HA from apparently pristine charcoals raises the question whether some HA could be derived via diagenetic alteration of charcoal itself. Here we address this question through comparison of freshly produced charcoal with samples from archaeological and geological sites exposed to environmental conditions for millennia using elemental (C/H/O) and isotopic (δ<sup>13</sup>C) measurements, Fourier Transform Infrared Spectroscopy (FTIR) and proton Liquid-State Nuclear Magnetic Resonance (<sup>1</sup>H NMR). The results of analyses show that the presence of highly carboxylated and aromatic alkali-extractable HA in charcoal from depositional environments can often be attributable to the effects of post-depositional processes, and that these substances can represent the products of post-depositional diagenetic alteration in charcoal

Isotopes in pyrogenic carbon: a review

Pyrogenic carbon (PC; also known as biochar, charcoal, black carbon and soot) derived from natural and anthropogenic burning plays a major, but poorly quantified, role in the global carbon cycle. Isotopes provide a fundamental fingerprint of the source of PC and a powerful tracer of interactions between PC and the environment. Radiocarbon and stable carbon isotope techniques have been widely applied to studies of PC in aerosols, soils, sediments and archaeological sequences, with the use of other isotopes currently less developed. This paper reviews the current state of knowledge regarding (i) techniques for isolating PC for isotope analysis and (ii) processes controlling the carbon (<sup>13</sup>C and <sup>14</sup>C), nitrogen, oxygen, hydrogen and sulfur isotope composition of PC during formation and after deposition. It also reviews the current and potential future applications of isotope based studies to better understand the role of PC in the modern environment and to the development of records of past environmental change

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

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.The Radiocarbon archives are made available by Radiocarbon and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform February 202

Charcoal reflectance measurements: implications for structural characterization and assessment of diagenetic alteration

Charcoal is a valuable source of archaeological and palaeoenvironmental proxy data. However growing\ud evidence suggests that production conditions can strongly influence post-depositional alteration of\ud charcoal. Consequently, both reconstruction of production temperature and understanding of the\ud potential for diagenetic alteration are of great interest. Here, we use mean random reflectance (R0-mean)\ud in conjunction with other chemical characterization methods to address these questions. R0-mean was\ud obtained for a suite of modern analogue charcoal, produced under controlled conditions, and for\ud a series of natural charcoal samples, obtained from archaeological and palaeoenvironmental deposits.\ud R0-mean proves to be a robust measure to assess formation temperature for samples produced at 400 C\ud and above, even after exposure to highly oxidizing conditions. R0-mean is also useful for samples formed\ud between 300 C and 400 C. However, if an assemblage of charcoals has been exposed to oxidizing\ud conditions, lower temperature charcoals may be preferentially lost. It is apparent that charcoal\ud produced at lower temperatures is more highly susceptible to chemical oxidation, and that there is\ud a continuum in charcoal degradation potential, dependant upon fuel material and production\ud conditions