Depth-dependent molecular composition and photo-reactivity of dissolved organic matter in a boreal lake under winter and summer conditions

Abstract. Transformations of dissolved organic matter (DOM) in boreal lakes lead to large greenhouse gas emissions as well as substantial carbon storage in sediments. Using novel molecular characterization approaches and photochemical degradation experiments we studied how seasonal patterns in water column stratification affected the DOM in a Swedish lake under early spring and summer conditions. Dissolved organic carbon (DOC) concentrations were consistently higher above the sediment when compared to surface waters throughout the sampling periods. Photobleaching alone could not explain this difference in DOC because the lake was covered by 40 cm-thick ice during late winter sampling and still showed the same DOC trend. The differences in the molecular diversity between surface DOM in winter and summer were consistent with ongoing photobleaching/decarboxylation and a possible bacterial consumption of photo-products. Additional photo-degradation experiments using simulated sunlight showed a production of highly oxidized organic molecules and low molecular weight compounds in all late winter samples and also in the deep water sample in summer. In the surface summer DOM sample, few such molecules were produced during the photo-degradation experiments, confirming that DOM was already photobleached prior to the experiments. This study suggests that photobleaching, and therefore also the ice cover during winter, plays a central role in surface DOM transformation, with important differences in the molecular composition of DOM between surface and deep boreal lake waters. The release of DOC from boreal lake sediments also contribute to this pattern. Photochemical degradation of DOM may be more extensive following ice-out and water column turnover when non-light exposed and thereby photosensitive DOM is photo-mineralized. Hence, the yearly DOM photo-mineralization may be greater than inferred from studies of recently light-exposed DOM.