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

Stabilization of extracellular polymeric substances (Bacillus subtilis) by adsorption to and coprecipitation with Al forms

Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction results in a decrease in EPS bioaccessibility, it may contribute to stabilization of microbial-derived organic carbon (OC) in soil. Here we examined: (i) the chemical fractionation of EPS produced by a common Gram positive soil bacterial strain (Bacillus subtilis) during reaction with dissolved and colloidal Al species and (ii) the resulting stabilization against desorption and microbial decay by the respective coprecipitation (with dissolved Al) and adsorption (with Al(OH)3(am)) processes. Coprecipitates and adsorption complexes obtained following EPS-Al reaction as a function of pH and ionic strength were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The stability of adsorbed and coprecipitated EPS against biodegradation was assessed by mineralization experiments for 1100 h. Up to 60% of the initial 100 mg/L EPS-C was adsorbed at the highest initial molar Al:C ratio (1.86), but this still resulted only in a moderate OC mass fraction in the solid phase (17 mg/g Al(OH)3(am)). In contrast, while coprecipitation by Al was less efficient in removing EPS from solution (maximum values of 33% at molar Al:C ratios of 0.1-0.2), the OC mass fraction in the solid product was substantially larger than that in adsorption complexes. Organic P compounds were preferentially bound during both adsorption and coprecipitation. Data are consistent with strong ligand exchange of EPS phosphoryl groups during adsorption to Al(OH)3(am), whereas for coprecipitation weaker sorption mechanisms are also involved. X-ray photoelectron analyses indicate an intimate mixing of EPS with Al in the coprecipitates, which is not observed in the case of EPS adsorption complexes. The incubation experiments showed that both processes result in overall stabilization of EPS against microbial decay. Stabilization of adsorbed or coprecipitated EPS increased with increasing molar Al:C ratio and biodegradation was correlated with EPS desorption, implying that detachment of EPS from surface sites is a prerequisite for microbial utilization. Results indicate that the mechanisms transferring EPS into Al-organic associations may significantly affect the composition and stability of biomolecular C, N and P in soils. The observed efficient stabilization of EPS might explain the strong microbial character of organic matter in subsoils