Modern and fossil charcoal: aspects of structure and diagenesis

The structures and compositions of modern and fossil charcoal samples were compared in order to evaluate charcoal degradation processes in archaeological sites. Modern charcoal samples produced in campfires contain two major phases: graphite-like microcrystallites and a non-organized phase. These phases create a mosaic-like structure with differing relative proportions depending on the taxonomic source of the wood used. Fossil charcoal samples (Tel Dor, Israel: 3000 years BP and Kebara Cave, Israel: 40,000 years BP) also contained the graphite-like microcrystallites and the non-organized phases, but were clearly altered compared to modern charcoal. The graphite-like phase of the fossil charcoal has much higher electrical resistivity, and its ESR properties show that it has markedly altered surface electronic states. Infrared spectra show the presence of additional carboxylate groups. Oxidation has therefore altered the structure. This appears to be a “self-humification” process that affects the graphitic component, and probably the non-organized phase as well.     

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