Bacterial and abiotic decay in waterlogged archaeological Picea abies (L.) Karst studied by confocal Raman imaging and ATR-FTIR spectroscopy

Abstract Waterlogged archaeological Norway spruce [ Picea abies (L.) Karst] poles were studied by means of confocal Raman imaging (CRI) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) analysis to determine lignin and polysaccharide composition and distribution in the cell wall. The waterlogged archaeological wood (WAW) was submerged under anoxic conditions for approximately 400 years and solely decayed by erosion bacteria (EB). CRI showed that decayed tracheids contain a residual material (RM) with heterogeneous lignin distribution; within the same tracheid RM often contained regions with intensities lower than sound S2 layers up to intensity values as high as the compound middle lamella (CML). CRI revealed strong depletion of carbohydrates in RM which indicated that EB are able to utilise the carbohydrate fraction of the cell wall effectively. Raman bands assigned to lignin did not show any difference between RM and sound S2. This is a hint that EB do not modify the lignin structure. Sound WAW free from EB decay showed evidence of loss of acetyl groups in glucomannan, loss of un-conjugated ester linkages in the lignin-carbohydrate complexes between xylan and lignin, and minor oxidation of the lignin polymer compared to recent reference material. This is evidence for abiotic decay in the course of waterlogging.