Dissolved organic matter and its parent organic matter in grass upland soil horizons studied by analytical pyrolysis techniques

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Abstract
Summary: We have sought to understand the molecular mechanisms by which dissolved organic matter (DOM) forms and soil organic matter (SOM) degrades in upland peaty gley soil under grass. Pyrolysis mass spectrometry (Py‐MS) and pyrolysis gas chromatography mass spectrometry (Py‐GC/MS) were applied to characterize the DOM collected from lysimeters and its parent SOM. The macromolecular organic matter in the litter and fermentation (Lf) horizon of the soil consists primarily of little decomposed lignocellulose from grass, whereas the humus (Oh) horizon is characterized by an accumulation of selectively decomposed lignocellulose material, microbial metabolites and bound fatty acids. The mineral horizon produced a relative enrichment of furan structures derived from microbial reworking of plant polysaccharides but virtually no lignin signals. A series of exceptional long chain C43to C53fatty acids with odd over even predominance, probably derived from mycobacteria, were also identified in the Oh horizon. Side‐chain oxidation and shortening, increase of carboxyl functionality and selective removal of syringyl (S) > guaiacyl (G) > p‐hydroxyphenyl (P) lignin units were the main reactions when lignin degraded. Compared with SOM, the DOM shows a large accumulation of more oxidized lignin and aromatic structures, especially those containing carboxylic and dicarboxylic acid functionalities and with shorter side‐chain length. The polysaccharide‐type compounds in the DOM were more modified (greater abundance of furan structures in pyrolysis products), and had significantly lower molecular weight and more diverse polymeric structures than did those in soils. Increased temperature and rainfall appeared to result in greater relative abundance of lignin degradation products and aromatic compounds in DOM.