The effect of charring and burial on the biochemical composition of cereal grains: investigating the integrity of archaeological plant material

Stable isotope analysis of charred archaeobotanical cereal grains has the potential to provide direct evidence of crop growing conditions in the past and to refine palaeodietary predictions. If isotope values of archaeobotanical material are to be considered robust, it is necessary to characterise the compositional changes associated with their charring and burial. This study used a suite of analytical techniques, including FT-IR and solid state ¹³C NMR, to characterise changes in the biochemical composition of modern einkorn grains with heating at 230 °C for 2 h, 4 h, 8 h and 24 h, encompassing conditions that replicate their undistorted ancient counterparts. The biochemical composition of archaeobotanical charred einkorn grains was also investigated by FT-IR and solid state ¹³C NMR in order to assess the changes in composition which occur during burial. Results of FT-IR and solid-state ¹³C NMR show that heating of modern einkorn grains resulted in Maillard reactions between cereal proteins and starch, forming high molecular weight melanoidins, which contain both alkyl and aromatic carbon. Loss of low molecular weight carbon and nitrogen-containing volatiles resulted in a slight but non-systematic increase in the δ¹³C values and a systematic increase of 0.8‰ in the δ¹⁵N values of the charred einkorn grains. Solid-state ¹³C NMR shows that the ancient charred einkorn grains consisted entirely of aromatic carbon and retained a similar proportion of nitrogen to their modern 24 h charred counterparts, despite a significantly lower concentration of amino acids. This indicates that the amino acid nitrogen in the ancient charred grains was retained in the stable melanoidins whose polymeric structure makes them resistant to subsequent degradation.