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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.

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.

Dissolved Organic Matter (DOM) represents a mixture of organic molecules that vary due to different source materials and degree of processing. Characterizing how DOM composition evolves along the aquatic continuum can be difficult. Using a size-exclusion chromatography technique (LC-OCD), we assessed the variability in DOM composition from both surface and groundwaters across a number of Canadian ecozones (mean annual temperature spanning −10 to +6 C). A wide range in DOM concentration was found from 0.2 to 120 mg C/L. Proportions of different size-based groupings across ecozones were variable, yet similarities between specific water-body types, regardless of location, suggest commonality in the processes dictating DOM composition. A PCA identified 70% of the variation in LC-OCD derived DOM compositions could be explained by the water-body type. We find that DOM composition within a specific water-body type is similar regardless of the differences in climate or surrounding vegetation where the sample originated from.HighlightsSize-exclusion chromatography (using LC-OCD) is a fast and effective tool to quantify differences in DOM composition across different environmentsProportions of biopolymers and low molecular weight fractions can distinguish between surface and groundwater DOMSimilar water-body types have comparable DOM size compositions across ecozones that range in annual air temperatures from –10 to 6ºC

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 base-flow conditions in a boreal region of Quebec (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 hotspot 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 hubstances contributing roughly equally to these fluvial emissions.