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Dissolved organic matter (DOM) is recognized for its importance in freshwater ecosystems, but historical reliance on DOM quantity rather than indicators of DOM composition has led to an incomplete understanding of DOM and an underestimation of its role and importance in biogeochemical processes. A single sample of DOM can be composed of tens of thousands of distinct molecules. Each of these unique DOM molecules has their own chemical properties and reactivity or role in the environment. Human activities can modify DOM composition and recent research has uncovered distinct DOM pools laced with human markers and footprints. Here we review how land use change, climate change, nutrient pollution, browning, wildfires, and dams can change DOM composition which in turn will affect internal processing of freshwater DOM. We then describe how human-modified DOM can affect biogeochemical processes. Drought, wildfires, cultivated land use, eutrophication, climate change driven permafrost thaw, and other human stressors can shift the composition of DOM in freshwater ecosystems increasing the relative contribution of microbial-like and aliphatic components. In contrast, increases in precipitation may shift DOM towards more relatively humic-rich, allochthonous forms of DOM. These shifts in DOM pools will likely have highly contrasting effects on carbon outgassing and burial, nutrient cycles, ecosystem metabolism, metal toxicity, and the treatments needed to produce clean drinking water. A deeper understanding of the links between the chemical properties of DOM and biogeochemical dynamics can help to address important future environmental issues, such as the transfer of organic contaminants through food webs, alterations to nitrogen cycling, impacts on drinking water quality, and biogeochemical effects of global climate change.

The balance of organic carbon (OC), nitrogen (N) and phosphorus (P) plays a crucial role in determining the processing, retention, and movement of these solutes across the aquatic continuum. Floods and droughts can significantly alter the quantity and ratios of OC:N:P export within inland waters, but how these ratios change, and are coupled within watersheds that integrate rivers and lakes, is not well known. We investigated the stoichiometry and export of dissolved organic carbon (DOC), total N (TN) and total P (TP) in two lake watersheds (10 inflows, 2 outflows) in the southern Boreal Shield over a 37‐year period. Although DOC, TN, and TP concentration behaved similarly, DOC:TN:TP ratios varied seasonally, strongly modulated by stream discharge. DOC:TN, DOC:TP and TN:TP export initially increased rapidly with increasing discharge, peaking at 10%–20% exceedance of the annual discharge for DOC:TP and TN:TP ratios, indicating a rapid depletion of catchment OC sources. Both flood and low flow events resulted in lower DOC:TN and lower DOC:TP export—thereby increasing the relative contributions of stream TN and TP. Consequently, elevated annual discharge coupled with infrequent but high floods and periods of low flow events increased the contributions of TN and TP relative to DOC. Overall, the lakes retained DOC, while increasing TN relative to TP. Nonetheless, the flow regime played a role in modulating nutrient retention in the lakes, likely due to changes in residence time, and the interplay of physical, photochemical, and biological degradation processes. Plain Language Summary How floods and droughts affect the relationship between organic carbon (OC) and nitrogen and phosphorus in terms of their alteration, removal from, or storage within, river and lake environments is not well known. We investigated two lake watersheds with their 10 inflowing and 2 outflowing streams over 37 years. The ratios of the OC to nutrients changed seasonally and were affected by intra‐annual stream flow variability. Slightly higher than average flows (10%–20% higher) initially increased the amount of OC that was exported from the watershed compared to nitrogen and phosphorus, but this export was notably lower during low flows and floods. This highlights the effects of extremely high and low flows, resulting in increased nitrogen and phosphorus in the streams. Internal processing by lakes generally decreased OC, while adding nitrogen relative to phosphorus, however the lakes retained less OC and phosphorus when the number of annual floods increased. This is important as the frequency and intensity of floods and droughts are predicted to increase in the future which may change how nutrients are altered and removed along the inland‐marine aquatic continuum. These potential changes could impact aquatic ecosystems and the ecosystem services they provide. Key Points Our long‐term data set provides a robust perspective on patterns in watershed‐scale stoichiometry and organic carbon and nutrient transport Flow regimes (floods and periods of low flow) are critical in shaping nutrient and organic carbon stoichiometry in aquatic ecosystems Lakes play an important role in nutrient and organic carbon removal within a stream network

Here for the first time, we analyze the concentration of dissolved (DOC) and particulate organic carbon (POC), as well as its optical properties (absorbance and fluorescence) from several proglacial streams across Iceland, the location of Europe’s largest non-polar ice cap. We found high spatial variability of DOC concentrations and dissolved organic matter (DOM) composition during peak melt, sampling 13 proglacial streams draining the 5 main Icelandic glaciers. Although glacial-derived organic matter (OM) was dominated by proteinaceous florescence, organic matter composition was variable among glaciers, often exhibiting relatively higher aromatic content and increased humification (based on absorbance and fluorescence measurements) closer to the glacier terminus, modulated by the presence of glacial lakes. Additional sampling locations the in flow path of the river Hvitá revealed that while POC concentrations decreased downstream, DOC concentrations and the autochthonous fraction of OM increased, suggesting the reworking of the organic carbon by microbial communities, with likely implications for downstream ecosystems as glaciers continue to melt. Based on our measured DOC concentrations ranging from 0.11 mg·L−1 to 0.94 mg·L−1, we estimate a potential annual carbon release of 0.008 ± 0.002 Tg·C·yr−1 from Icelandic glaciers. This non-conservative first estimate serves to highlight the potentially significant contribution of Icelandic pro-glacial streams to the global carbon cycle and the need for the quantification and determination of the spatio-temporal variation of DOC and POC fluxes and their respective drivers, particularly in light of increased rates of melting due to recent trends in climatic warming.

Streams are significant sources of CO 2 to the atmosphere. Estimates of CO 2 evasion fluxes ( f CO2 ) from streams typically relate to the free flowing water but exclude geomorphological structures within the stream corridor. We found that gravel bars (GBs) are important sources of CO 2 to the atmosphere, with on average more than twice as high f CO2 as those from the streamwater, affecting f CO2 at the level of entire headwater networks. Vertical temperature gradients resulting from the interplay between advective heat transfer and mixing with groundwater within GBs explained the observed variation in f CO2 from the GBs reasonably well. We propose that increased temperatures and their gradients within GBs exposed to solar radiation stimulate heterotrophic metabolism therein and facilitate the venting of CO 2 from external sources (e.g. downwelling streamwater, groundwater) within GBs. Our study shows that GB f CO2 increased f CO2 from stream corridors by [median, (95% confidence interval)] 16.69%, (15.85–18.49%); 30.44%, (30.40–34.68%) and 2.92%, (2.90–3.0%), for 3 rd , 4 th and 5 th order streams, respectively. These findings shed new light on regional estimates of f CO2 from streams, and are relevant given that streamwater thermal regimes change owing to global warming and human alteration of stream corridors.

Streams are significant sources of CO to the atmosphere. Estimates of CO evasion fluxes (f ) from streams typically relate to the free flowing water but exclude geomorphological structures within the stream corridor. We found that gravel bars (GBs) are important sources of CO to the atmosphere, with on average more than twice as high f as those from the streamwater, affecting f at the level of entire headwater networks. Vertical temperature gradients resulting from the interplay between advective heat transfer and mixing with groundwater within GBs explained the observed variation in f from the GBs reasonably well. We propose that increased temperatures and their gradients within GBs exposed to solar radiation stimulate heterotrophic metabolism therein and facilitate the venting of CO from external sources (e.g. downwelling streamwater, groundwater) within GBs. Our study shows that GB f increased f from stream corridors by [median, (95% confidence interval)] 16.69%, (15.85-18.49%); 30.44%, (30.40-34.68%) and 2.92%, (2.90-3.0%), for 3 , 4 and 5 order streams, respectively. These findings shed new light on regional estimates of f from streams, and are relevant given that streamwater thermal regimes change owing to global warming and human alteration of stream corridors.