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.

The idea that small amounts of labile organic carbon might trigger the degradation of previously unreactive organic matter has attracted increasing scientific interest across multiple disciplines. Although this phenomenon, referred to as priming, has been widely reported in soils, evidence in freshwater systems is scarce and inconclusive. Here, we use a multifactorial microcosm experiment to test the conditions under which priming may be observed in freshwater ecosystems. We assessed the effect of pulse additions of three labile carbon sources (acetate, glucose, and cellobiose) on dissolved organic carbon (DOC) consumption using water from lakes with different trophic states (eutrophic to oligotrophic and clear to brownwater lakes). We further analyzed the effect of nutrient availability and the role of attachment of cells to surfaces. Despite the range of conditions tested, we found no clear evidence of a priming effect on DOC degradation, indicating that priming in freshwater systems may be of limited importance.

Northern high-latitude lakes are undergoing climate-induced changes including shifts in their hydrologic connectivity with terrestrial ecosystems. How this will impact dissolved organic matter (DOM) biogeochemistry remains uncertain. We examined the drivers of DOM composition for lakes in the Yukon Flats Basin in Alaska, an arid region of low relief that is characteristic of over one-quarter of circumpolar lake area. Utilizing the vascular plant biomarker lignin, chromophoric dissolved organic matter (CDOM), and ultrahigh-resolution mass spectrometry, we interpreted DOM compositional changes using lake-water stable isotope (δ 18 O-H 2 O) composition as a proxy for lake hydrologic connectivity with the landscape. We observed a relative decrease in CDOM in more hydrologically isolated lakes (enriched δ 18 O-H 2 O) without a corresponding decrease in dissolved organic carbon (DOC) concentration. Although DOC and CDOM were weakly correlated, a significant positive relationship between lignin and CDOM (r 2 = 0.67) demonstrates that optical parameters are useful for estimating lignin concentration and thus vascular plant contribution to lake DOM. Indicators of allochthonous DOM, including lignin carbon normalized yields, CDOM aromaticity proxies, and relative abundances of polyphenolic and condensed aromatic compound classes, were negatively correlated with δ 18 O-H 2 O (r 2 > 0.45), suggesting there is little allochthonous DOM supplied to many of these hydrologically isolated lakes. We conclude that decreased lake hydrologic connectivity, driven by ongoing climate change (i.e., decreased precipitation, warming temperatures), will reduce allochthonous DOM contributions and shift lakes toward lower CDOM systems with ecosystem-scale ramifications for heat transfer, photochemical reactions, productivity, and ultimately their biogeochemical function.

Agricultural impacts on aquatic ecosystems are well studied; however, most research has focused on temperate regions, whereas the forefront of agricultural expansion is currently in the tropics. At the vanguard of this growth is the boundary between the Amazon and Cerrado biomes in Brazil, driven primarily by expansion of soybean and corn croplands. Here we examine the impacts of cropland expansion on receiving lowland Amazon Basin headwater streams in terms of dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition via ultrahigh‐resolution mass spectrometry. Streams draining croplands had lower DOC concentrations and DOM molecular signatures enriched in N‐ and S‐containing formula in comparison to forested streams. Cropland streams were also enriched in aliphatic, peptide‐like, and highly unsaturated and phenolic (low O/C) compound categories in comparison to forest streams (enriched in polyphenolics, condensed aromatics, and highly unsaturated and phenolic [high O/C] compound categories) indicative of the shifting of sources from organic‐rich surface soils and litter layers to autochthonous and more microbial biomass. Distinct molecular assemblages were strongly correlated with cropland and forest catchments, highlighting headwater streams as sentinels for detecting change. On investigation of unique molecular formulae present in only cropland sites, four cropland markers provided the ability to track agricultural impacts in the region. Overall, these patterns indicate reduced organic matter inputs in croplands and greater microbial degradation at these sites leading to declining DOC concentrations, and DOM of more microbial character in receiving streams that is more biolabile, with clear ramifications for downstream ecology and biogeochemical cycles.

Pan‐Arctic riverine dissolved organic carbon (DOC) fluxes represent a major transfer of carbon from land‐to‐ocean, and past scaling estimates have been predominantly derived from the six major Arctic rivers. However, smaller watersheds are constrained to northern high‐latitude regions and, particularly with respect to the Eurasian Arctic, have received little attention. In this study, we evaluated the concentration of DOC and composition of dissolved organic matter (DOM) via optical parameters, biomarkers (lignin phenols), and ultrahigh resolution mass spectrometry in the Northern Dvina River (a midsized high‐latitude constrained river). Elevated DOC, lignin concentrations, and aromatic DOM indicators were observed throughout the year in comparison to the major Arctic rivers with seasonality exhibiting a clear spring freshet and also some years a secondary pulse in the autumn concurrent with the onset of freezing. Chromophoric DOM absorbance at a350 was strongly correlated to DOC and lignin across the hydrograph; however, the relationships did not fit previous models derived from the six major Arctic rivers. Updated DOC and lignin fluxes were derived for the pan‐Arctic watershed by scaling from the Northern Dvina resulting in increased DOC and lignin fluxes (50 Tg yr−1 and 216 Gg yr−1, respectively) compared to past estimates. This leads to a reduction in the residence time for terrestrial carbon in the Arctic Ocean (0.5 to 1.8 years). These findings suggest that constrained northern high‐latitude rivers are underrepresented in models of fluxes based from the six largest Arctic rivers with important ramifications for the export and fate of terrestrial carbon in the Arctic Ocean.