@article {Zigah2017, title = {Constraining the sources and cycling of dissolved organic carbon in a large oligotrophic lake using radiocarbon analyses}, journal = {Geochimica et Cosmochimica Acta}, volume = {208}, year = {2017}, pages = {102-118}, abstract = {Abstract We measured the concentrations and isotopic compositions of solid phase extracted (SPE) dissolved organic carbon (DOC) and high molecular weight (HMW) \{DOC\} and their constituent organic components in order to better constrain the sources and cycling of \{DOC\} in a large oligotrophic lacustrine system (Lake Superior, North America). \{SPE\} \{DOC\} constituted a significant proportion (41-71\%) of the lake \{DOC\} relative to \{HMW\} \{DOC\} (10-13\%). Substantial contribution of 14C-depleted components to both \{SPE\} \{DOC\} (Δ14C = 25 to 43{\textperthousand}) and \{HMW\} \{DOC\} (Δ14C = 22 to 32{\textperthousand}) was evident during spring mixing, and depressed their radiocarbon values relative to the lake dissolved inorganic carbon (DIC; Δ14C \~{} 59{\textperthousand}). There was preferential removal of 14C-depleted (older) and thermally recalcitrant components from \{HMW\} \{DOC\} and \{SPE\} \{DOC\} in the summer. Contemporary photoautotrophic addition to \{HMW\} \{DOC\} was observed during summer stratification in contrast to \{SPE\} DOC, which decreased in concentration during stratification. Serial thermal oxidation radiocarbon analysis revealed a diversity of sources (both contemporary and older) within the \{SPE\} DOC, and also showed distinct components within the \{HMW\} DOC. The thermally labile components of \{HMW\} \{DOC\} were 14C-enriched and are attributed to heteropolysaccharides (HPS), peptides/amide and amino sugars (AMS) relative to the thermally recalcitrant components reflecting the presence of older material, perhaps carboxylic-rich alicyclic molecules (CRAM). The solvent extractable lipid-like fraction of \{HMW\} \{DOC\} was very 14C-depleted (as old as 1270-2320 14C years) relative to the substances isolated by acid hydrolysis of \{HMW\} DOC. Our data constrain relative influences of contemporary \{DOC\} and old DOC, and \{DOC\} cycling in a modern freshwater ecosystem.}, keywords = {atmospheric co2, Carbohydrate-like substance, Carboxylic-rich alicyclic molecules (CRAM), Contemporary DOC, dissolved inorganic carbon, dissolved organic carbon, Freshwater carbon cycling, Heteropolysaccharides (HPS), High molecular weight DOC, Lake Superior, Lipid-like fraction, Old DOC, Oligotrophic lake, Protein-like substance, radiocarbon, Serial thermal oxidation, Solid phase extracted DOC, Stable isotope, Unhydrolysable material}, issn = {0016-7037}, doi = {10.1016/j.gca.2017.03.021}, url = {http://www.sciencedirect.com/science/article/pii/S0016703717301722}, author = {Prosper K. Zigah and Elizabeth C. Minor and Ann P. McNichol and Li Xu and Josef P. Werne} }