Molecular-level dissolved organic matter dynamics in lakes Constraints on reactivity and persistence

Abstract: Dissolved organic matter (DOM) is a central component of the global carbon cycle. Thus, small changes to the amount of DOM imported, processed and produced within lakes can have a large effect on regional carbon budgets. In addition to being a vital energy source at the base of the aquatic food web, DOM is physico-chemically reactive. However, identifying and understanding the controls of DOM processing has remained challenging due to the complex composition of DOM. DOM comprises a mixture of decomposition by-products of terrestrial origin as well as newly synthesized material from in situ production. DOM compounds form gradients of reactivity to biogeochemical processes, such as photodegradation, biodegradation, and flocculation, and they perform a suite of functions in aquatic systems. The overarching goal of this thesis was to investigate controls of DOM processing in Swedish lakes. We do this in two ways: 1) by characterizing the molecular-level composition of DOM in lakes, and 2) by investigating interactions between very labile and relatively recalcitrant DOM. The first three chapters utilize ultrahigh resolution mass spectrometry to show that the detailed chemical composition of DOM varies along a hydrology gradient, and secondarily along a temperature gradient that co-varies with agriculture and nutrients. Next, we illustrate the coherence between molecular-level characteristics and bulk optical characteristics. Together, these studies suggest that protein-like fluorescence, aliphatic compounds, and N-containing compounds are either resistant to degradation or tightly cycled in the system, and thus persist at long water residence times. The most oxidized compounds, such as vascular plant-derived polyphenolic compounds, are abundant in areas with high precipitation and are lost with increasing water residence time. Vascular plant-derived polyphenolic compounds were most strongly related to DOM with high apparent molecular weight, suggesting that hydrophobic interactions drive aggregate formation. Furthermore, the association of high molecular weight DOM with polyphenolic compounds suggests that aggregates are hotspots of reactivity in aquatic systems. Finally, we find no indication that the addition of labile organic matter enhances the biodegradation of less reactive DOM. Thus, we suggest that in freshwaters, intrinsic molecular properties, such as the basic structural features of compounds, dominate over extrinsic factors.