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The net accumulation of remains of Sphagnum spp. is fundamental to the development of many peatlands. The effect of polyphenols from Sphagnum on decomposition processes is frequently cited but has barely been studied. The central area of the Rodmossamyran peatland (Sweden) is an open lawn that consists mostly of Sphagnum spp. with a very low contribution from vascular plants. In order to determine the effects of decay on sphagnum phenols, 53 samples of a 2.7 m deep core from this lawn were analysed with pyrolysis gas chromatography–mass spectrometry (pyrolysis-GC–MS) and compared with more traditional decomposition proxies such as C/N ratio, UV light transmission of alkaline peat extracts, and bulk density. Factor analysis of 72 quantified pyrolysis products suggested that the variation in 4-isopropenylphenol was largely determined by aerobic decomposition instead of Sphagnum abundance. In order to evaluate the effects of aerobic decay in Sphagnum peat, down-core records from different climatic regions were compared using molecular markers for plant biopolymers and C/N ratio. These included markers for lignin from vascular plants ((di)methoxyphenols), polyphenols from Sphagnum spp. (4-isopropenylphenol), and cellulose (levoglucosan). Our results indicate that polyphenols from Sphagnum are preferentially degraded over polysaccharides; consequently the variability of the marker for sphagnum acid, 4-isopropenylphenol, was found indicative of decomposition instead of reflecting the abundance of Sphagnum remains. The fact that 4-isopropenylphenol is aerobically degraded in combination with its specificity for Sphagnum spp. makes it a consistent indicator of past hydrological conditions in Sphagnum-dominated peat. In contrast, the variability of C/N records in Sphagnum-dominated peat was influenced by both vegetation shifts and decomposition, and the dominant effect differed between the studied peatlands. Our results provide direction for modelling studies that try to predict possible feedback mechanisms between peatlands and future climate change, and indicate that the focus in Sphagnum decay studies should be on carbohydrates rather than on phenolic compounds.

Differences in soil organic matter (SOM) composition in consecutive soil profiles (under algae, grass, moss, heather and pine) from a primary vegetation succession (central Netherlands) were investigated by Cross Polarization-Magic Angle Spinning (CPMAS) 13C NMR, chemical degradation (acid hydrolysis of polysaccharides) and pyrolysis-GC/MS (Py-GC/MS) in relation to the vegetation. All mineral soil horizons had lower contents of polysaccharides than the ectorganic layer and/or the fresh plant material as suggested by the diminishing O-alkyl peaks by NMR. The monosaccharide distribution pointed to an increase of microbial sugars in the soil as suggested by the raising C6/C5 ratios. Soil polysaccharides may be accompanied by a significant contribution of carbohydrates from mosses in the first stages, because the undecomposed moss tissues have high C6/C5 ratios, which falsify the usual interpretation that such high ratios may be due to microbial sugars. Fresh litter and ectorganic layers under heather and pine had similar contents of aromatics, but the contribution of lignin (guaiacols and syringols) was lower in the ectorganic horizons. The degree of oxidation, as determined by the acid/aldehyde ratio, increased with progressive humification. All Ah horizons contained less aromatics, more oxidized lignin remnants and higher amounts of aliphatic compounds than the litter. One or two macromolecules, which produced n-alkenes/n-alkanes and branched alkenes/alkanes upon pyrolysis and were derived from mosses, were mainly responsible for the accumulation of aliphatics in soil, although other aliphatic polymers, such as suberin, might also play an important role. Preservation of components from earlier vegetation might significantly influence SOM composition.

Analytical pyrolysis-GC/MS and solid-state 13C NMR (nuclear magnetic resonance) were applied to the NaOH-extractable organic matter fraction of a colluvial soil from Galicia (NW Spain) that represents more than 8500 yr of accumulation. While molecular indicators of vegetation change were looked for, it seemed likely that any such signal was disturbed by the intense fire regime of the area. This conclusion was drawn from (1) the presence of three charcoal layers, (2) the high proportion of aryl C in NMR spectra (non-quantitative) and (3) the prevalence of benzenes and polycyclic aromatic hydrocarbons (PAHs) in the chromatograms (38 ± 6% of total identified peak area), also in charcoal-poor samples. If this conclusion is accurate, the area has been subjected to burning episodes for at least 8000 yr. Additionally, the results indicate that biomass burning residues (black carbon; BC) may become NaOH extractable after long periods of degradation in mineral soil. These results add to our knowledge of the long-term fate of BC in soil, which is a potential agent in the global C cycle., Project supported by the "Plan Nacional: Paleopaisaje y prehistoria del Futuro Parque de Arte Rupestre de Campo Lameiro, Pontevedra" (PGIDT02CCP60601).

Publisher Summary Molecular chemistry reveals significant differences between extracted and non-extractable (residue) peat. In the extracts, lignin and other aromatic fragments, nitrogen-containing moieties are more abundant whereas aliphatics, methyl ketones and lipids are more abundant in the non-extractable fraction. This is not astonishing, since partly oxidized lignin and proteins are hydrophilic and extractable with NaOH, whereas for the extraction of lipids one needs organic solvents. Short-chain straight aliphatics are more abundant in the extractable fraction, and there appears to be a regular decay series of alkanes and alkenes from n -C 28, 28:1 to n -C 10 . One branched alkane that is predominantly present in the extractable fraction is possibly of microbial origin. Some polysaccharide moieties are specifically associated with the extractable fraction and some with the residues. This probably reflects a predominantly microbial origin for the first and predominantly plant-derived for the second, because the plant-derived polysaccharides may still be present in larger molecular units.