Origin of dissolved organic matter in the Harz Mountains (Germany): A thermally assisted hydrolysis and methylation (THM-GC–MS) study

Environmental change is increasing the concentration of dissolved organic matter (DOM) in catchments of the Northern Hemisphere. This study aims to assess the causes of high DOM concentrations in streams and reservoirs of the Harz National Park (Germany), by means of molecular characterization using thermally assisted hydrolysis and methylation (THM-GC–MS). In order to formulate proxies of the prevailing origin of the numerous THM products of polyphenols, carbohydrates, proteins, aliphatic macromolecules, resins and other DOM precursors, we created a reference sample set of potential sources (spruce, birch, blueberry, heather, peat moss, soils) from the area. Besides solid-state reference samples (bulk organic matter; BOM) we obtained and analyzed their leachates (water-extractable OM; WEOM). Finally, an existing THM-GC–MS dataset of the DOM from the Oder river, which crosses the boundary between peat and forest biomes in the Harz, was extended and explored chemometrically using Principal Component Analysis (PCA) to test the proxies for stream DOM assessment. The results show large differences between BOM and WEOM, which suggests that the solid-to-leachate transition is highly selective or significantly alters the major biomolecular constituents. THM compounds that tend to be more abundant in WEOM than in BOM are G-type phenolic compounds (1,2-dimethoxybenzenes, from lignin and tannin), nitrogen-containing moieties and benzene carboxylic acids, whereas WEOM is depleted in products of polysaccharides, syringyl lignin and aliphatic macromolecules (cutin and suberin). The lignin fingerprint of the WEOM also differs significantly from that of BOM, being depleted in the vast majority of the typical products of macromolecular lignin (G7, G8, G14, G15) and enriched in the acid moiety (G6, predominantly from vanillic acid), especially for spruce wood. THM chromatograms of DOM from the forest section of the Oder show an extraordinary abundance of G6, most probably from spruce-derived lignin. This may indicate a major ...