Soils export large amounts of organic matter to rivers, and there are still major uncertainties concerning the composition and reactivity of this material and its fate within the fluvial network. Here we reconstructed the pattern of movement and processing of dissolved organic matter (DOM) along a soil‐stream‐river continuum under summer baseflow conditions in a boreal region of Québec (Canada), using a combination of fluorescence spectra, size exclusion chromatography and ultrahigh resolution mass spectrometry. Our results show that there is a clear sequence of selective DOM degradation along the soil‐stream‐river continuum, which results in pronounced compositional shifts downstream. The soil‐stream interface was a hot spot of DOM degradation, where biopolymers and low molecular weight (LMW) compounds were selectively removed. In contrast, processing in the stream channel was dominated by the degradation of humic‐like aromatic DOM, likely driven by photolysis, with little further degradation of either biopolymers or LMW compounds. Overall, there was a high degree of coherence between the patterns observed in DOM chemical composition, optical properties, and molecular profiles, and none of these approaches pointed to measurable production of new DOM components, suggesting that the DOM pools removed during transit were likely mineralized to CO2. Our first order estimates suggest that rates of soil‐derived DOM mineralization could potentially sustain over half of the measured CO2 emissions from this stream network, with mineralization of biopolymers and humic substances contributing roughly equally to these fluvial emissions.

Carbon dioxide (CO2) emissions from freshwater ecosystems are almost universally predicted to increase with climate warming. Glacier-fed rivers and lakes, however, differ critically from those in nonglacierized catchments in that they receive little terrestrial input of organic matter for decomposition and CO2 production, and transport large quantities of easily mobilized comminuted sediments available for carbonate and silicate weathering reactions that can consume atmospheric CO2. We used a whole-watershed approach, integrating concepts from glaciology and limnology, to conclusively show that certain glacier-fed freshwater ecosystems are important and previously overlooked annual CO2 sinks due to the overwhelming influence of these weathering reactions. Using the glacierized Lake Hazen watershed (Nunavut, Canada, 82°N) as a model system, we found that weathering reactions in the glacial rivers actively consumed CO2 up to 42 km downstream of glaciers, and cumulatively transformed the High Arctic’s most voluminous lake into an important CO2 sink. In conjunction with data collected at other proglacial freshwater sites in Greenland and the Canadian Rockies, we suggest that CO2 consumption in proglacial freshwaters due to glacial melt-enhanced weathering is likely a globally relevant phenomenon, with potentially important implications for regional annual carbon budgets in glacierized watersheds.

Northern high-latitude lakes are hotspots for cycling dissolved organic carbon (DOC) inputs from allochthonous sources to the atmosphere. However, the spatial distribution of lake dissolved organic matter (DOM) is largely unknown across Arctic-boreal regions with respect to the surrounding landscape. We expand on regional studies of northern high-latitude DOM composition by integrating DOC concentrations, optical properties, and molecular-level characterization from lakes spanning the Canadian Taiga to the Alaskan Tundra. Lakes were sampled during the summer from July to early September to capture the growing season. DOM became more optically processed and molecular-level aromaticity increased northward across the Canadian Shield to the southern Arctic and from interior Alaska to the Tundra, suggesting relatively greater DOM incorporation from allochthonous sources. Using water isotopes (δ 18 O-H 2 O), we report a weak overall trend of increasing DOC and decreasing aromaticity in lakes that were hydrologically isolated from the landscape and enriched in δ 18 O-H 2 O, while within-region trends were stronger and varied depending on the landscape. Finally, DOC correlated weakly with chromophoric dissolved organic matter (CDOM) across the study sites, suggesting that autochthonous and photobleached DOM were a major component of the DOC in these regions; however, some of the northernmost and wetland-dominated lakes followed pan-Arctic riverine DOC-CDOM relationships, indicating strong contributions from allochthonous inputs. As many lakes across the North American Arctic are experiencing changes in temperature and precipitation, we expect the proportions of allochthonous and autochthonous DOM to respond with aquatic optical browning with greater landscape connectivity and more internally produced DOM in hydrologically isolated lakes. Plain Language SummaryAs the Arctic responds to warming, permafrost thaw, and variations in precipitation, the distribution of carbon pools within northern high-latitude lakes will also change. Specifically, the composition of dissolved organic matter (DOM) and how it is altered and moved from the landscape to the atmosphere will be highly dependent on local precipitation patterns and hydrology, but these relationships are not well constrained across large regions. We sampled over 70 individual lakes during the summer spanning various ecoregions from interior Canada to the Alaskan Tundra and characterized their dissolved organic carbon (DOC) concentrations and DOM composition using bulk and molecular-level analysis. Overall, DOM from these lakes was highly influenced by aquatic primary production but increased in the relative proportion of terrestrially derived organic matter as lake setting transitioned from forests to shrublands above the tree line. We also report a weak relationship between increasing DOC and decreasing terrestrial DOM as lakes become more hydrologically isolated across the pan-Arctic; however, regional trends were stronger within forested sampling areas and weaker in...

Dissolved organic matter (DOM) is a ubiquitous component of aquatic systems, impacting aquatic health and drinking water quality. These impacts depend on the mixture of organic molecules that comprise DOM. Changing climates are altering both the amount and character of DOM being transported from the terrestrial system into adjacent surface waters, yet DOM composition is not monitored as often as overall concentration. Many DOM characterization methods exist, confounding comparison of DOM composition across different studies. The objective of this research is to determine which parameters in a suite of relatively simple and common DOM characterization techniques explain the most variability in DOM composition from surface and groundwater sites. Further, we create a simple visualization tool to easily compare compositional differences in DOM. A large number of water samples (n = 250) was analyzed from six Canadian ecozones for DOM concentration, ultraviolet-visible light absorbance, molecular size, and elemental ratios. Principal component analyses was used to identify quasi-independent DOM compositional parameters that explained the highest variability in the dataset: spectral slope, specific-UV absorbance at 255nm, humic substances fraction, and dissolved organic carbon to dissolved organic nitrogen ratio. A ‘Composition Wheel’ was created by plotting these four parameters as a polygon. Our results find similarities in DOM composition irrespective of site differences in vegetation and climate. Further, two main end-member Composition Wheel shapes were revealed that correspond to DOM in organic-rich groundwaters and DOM influenced by photodegradation. The Composition Wheel approach uses easily visualized differences in polygon shape to quantify how DOM evolves by natural processes along the aquatic continuum and to track sources and degradation of DOM.