Despite the small continental coverage of lakes, they are hotspots of carbon cycling, largely due to the processing of terrestrially derived dissolved organic matter (DOM). As DOM is an amalgam of heterogeneous compounds comprising gradients of microbial and physicochemical reactivity, the factors influencing DOM processing at the molecular level and the resulting patterns in DOM composition are not well understood. Here we show, using ultrahigh-resolution mass spectrometry to unambiguously identify 4,032 molecular formulae in 120 lakes across Sweden, that the molecular composition of DOM is shaped by precipitation, water residence time and temperature. Terrestrially derived DOM is selectively lost as residence time increases, with warmer temperatures enhancing the production of nitrogen-containing compounds. Using biodiversity concepts, we show that the molecular diversity of DOM, or chemodiversity, increases with DOM and nutrient concentrations. The observed molecular-level patterns indicate that terrestrially derived DOM will become more prevalent in lakes as climate gets wetter.

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Bacteria play a central role in the cycling of carbon, yet our understanding of the relationship between the taxonomic composition and the degradation of dissolved organic matter (DOM) is still poor. In this experimental study, we were able to demonstrate a direct link between community composition and ecosystem functioning in that differently structured aquatic bacterial communities differed in their degradation of terrestrially derived DOM. Although the same amount of carbon was processed, both the temporal pattern of degradation and the compounds degraded differed among communities. We, moreover, uncovered that low-molecular-weight carbon was available to all communities for utilisation, whereas the ability to degrade carbon of greater molecular weight was a trait less widely distributed. Finally, whereas the degradation of either low- or high-molecular-weight carbon was not restricted to a single phylogenetic clade, our results illustrate that bacterial taxa of similar phylogenetic classification differed substantially in their association with the degradation of DOM compounds. Applying techniques that capture the diversity and complexity of both bacterial communities and DOM, our study provides new insight into how the structure of bacterial communities may affect processes of biogeochemical significance.

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δC-dissolved organic carbon (DOC) and ΔC-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern ΔC-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δC-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific Ocean and Antarctic lakes) exhibited distinct molecular composition due to differences in extent of degradation. Across all sites and end-members studied, we find a consistent shift in composition with aging, highlighting the persistence of certain biomolecules concurrent with degradation time.