Comparison of different methods to determine the degree of peat decomposition in peat bogs

Peat humification or decomposition is a frequently used proxy to extract past time changes in hydrology and climate from peat bogs. During the past century several methods to determine changes in peat decomposition have been introduced. Most of these methods are operationally defined only and the chemical changes underlying the decomposition process are often poorly understood and lack validation. Owing to the chemically undefined nature of many humification analyses the comparison of results obtained by different methods is difficult. In this study we compared changes in peat decomposition proxies in cores of two peat bogs (Konigsmoor, KK; Kleines Rotes Bruch, KRB) from the Harz Mountains (Germany) using C/N ratios, Fourier transform infrared spectra absorption (FTIR) intensities, Rock Eval (R) oxygen and hydrogen indices, delta C-13 and delta N-15 isotopic signatures and UV-absorption (UV-ABS) of NaOH peat extracts. In order to explain parallels and discrepancies between these methods, one of the cores was additionally analysed by pyrolysis gas chromatography mass spectrometry (pyrolysis-GC-MS). Pyrolysis-GC-MS data provide detailed information on a molecular level, which allows differentiation of both changes attributed to decomposition processes and changes in vegetation. Principal component analysis was used to identify and separate the effects of changes in vegetation pattern and decomposition processes because both may occur simultaneously upon changes in bog hydrology. Records of decomposition proxies show similar historical development at both sites, indicating external forcing such as climate as controlling the process. All decomposition proxies except UV-ABS and delta N-15 isotopes show similar patterns in their records and reflect to different extents signals of decomposition. The molecular composition of the KK core reveals that these changes are mainly attributed to decomposition processes and to a lesser extent to changes in vegetation. Changes in the molecular composition indicate that peat decomposition in the KK bog is mainly characterized by preferential decomposition of phenols and polysaccharides and relative enrichment of aliphatics during drier periods. Enrichment of lignin and other aromatics during decomposition was also observed but showed less variation than polysaccharides or aliphatics, and presumably reflects changes in vegetation associated with changes in hydrology of the bogs. Significant correlations with polysaccharide and aliphatic pyrolysis products were found for C/N ratios, FTIR-band intensities and for hydrogen index values, supporting that these decomposition indices provide reasonable information. Correlations of polysaccharide and aliphatic pyrolysis products with oxygen index values and delta C-13 was weaker, assumingly indicating carboxylation of the peat during drier periods and enrichment of isotopically lighter peat components during decomposition, respectively. FTIR, C/N ratio, pyrolysis-GC-MS analyses and Rock Eval hydrogen indices appear to reflect mass loss and related changes in the molecular peat composition during mineralization best. Pyrolysis-GC-MS allows disentangling the decomposition processes and vegetation changes. UV-ABS measurements of alkaline peat extracts show only weak correlation with other decomposition proxies and pyrolysis results as they mainly reflect the formation of humic acids through humification and to a lesser extent mass loss during mineralization.