Assessment of bog-body tissue preservation by pyrolysis-gas chromatography/mass spectrometry

Flash pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) was used to assess the quality and mechanism of protein preservation in the tissue of Iron Age bog bodies from Lindow, UK, and south-eastern Drenthe, The Netherlands. Abundant pyrolysis products of the fresh skin tissue, including 2,5-diketopiperazines of Pro-Gly, Pro-Ala, Pro-Val, Pro-Pro and Hyp, were readily assigned to specific amino acid or dipeptide moieties. Comparison of the pyrolysates of the bog-body tissues with that of modern samples revealed qualitative similarities suggesting good preservation of the collagen and non-collagenous proteins in the ancient tissues. Examination of the pyrolysates of samples of fresh calf skin, which had been treated with various vegetable tanning agents, clearly revealed markers of non-hydrolysable tannins including 1,2-benzenediol, 1,3-benzenediol and 1,2,3-benzenetriol, although chromatographic quality inevitably diminished with increasing functionalization of the compounds. Such markers were not detected in the pyrolysates of the bog-body tissues. Instead 4-isopropenylphenol, a characteristic pyrolysis product of Sphagnum moss, was detected in both solvent-extracted and base-treated samples of tissue. The presence of 4-isopropenylphenol in the pyrolysates of the bog-body tissues provides evidence that their preservation involves reactions of amino acids with sphagnum acid, and possibly other agents derived from the peat. The study constitutes the first chemical characterization of the pyrolysis products of modern and ancient collagen.