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