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  1. Abstract

    The relative capacity for watersheds to eliminate or export reactive constituents has important implications on aquatic ecosystem ecology and biogeochemistry. Removal efficiency depends on factors that affect either the reactivity or advection of a constituent within river networks. Here, we characterized Damköhler number (Da) for dissolved organic carbon (DOC) uptake in global river networks. Da equals the advection to reaction timescale ratio and thus provides a unitless indicator for DOC reaction intensity during transport within river networks. We aim to demonstrate the spatial and temporal patterns and interplays among factors that determine DOC uptake across global river networks. We show that watershed size imposes a primary control on river network DOC uptake due to a three orders of magnitude difference in water residence time (WRT) between the smallest and largest river networks. DOC uptake capacity in tropical river networks is 2–6 times that in temperate and the Arctic river networks, coinciding with larger DOC removals in warm than in cold watersheds. River damming has a profound impact on DOC uptake due to significantly extended WRTs, particularly in temperate watersheds where most constructed dams are situated. Global warming is projected to increase river network DOC uptake by ca. 19% until year 2100 under the RCP4.5 scenario.

     
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  2. Abstract

    Sunlight can oxidize dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) in freshwaters. The importance of complete photooxidation, or photomineralization, as a sink for DOC remains unclear in temperate rivers, as most estimates are restricted to lakes, high latitude rivers, and coastal river plumes. In this study, we construct a model representing over 75,000 river reaches in the Connecticut River Watershed (CRW), USA, to calculate spectrally resolved photomineralization. We test the hypothesis that photomineralization is a negligible DOC sink across all reaches and flow conditions relative to DOC fluxes. Our model quantifies reaction rates and transport drivers within the river reaches for the ranges of flow conditions, incoming solar irradiance, and canopy cover shading observed throughout the year. Our model predicts average daily areal photomineralization rates ranging from 1.16 mg‐C m−2 day−1in low flow river reaches in the winter, to 18.33 mg‐C m−2 day−1in high flow river reaches during the summer. Even for high photomineralization fluxes, corresponding photomineralization uptake velocities are typically at least an order of magnitude smaller than those reported for other instream processes. We calculate DOC elimination by photomineralization relative to DOC fluxes through individual stream reaches as well as the entire riverine portion of the CRW. We find that relative photomineralization fluxes are highest in summer drought conditions in low order streams. In median flows and mean light intensities, for an average watershed travel distance, 3%–5% of the DOC fluxes are eliminated, indicating that photomineralization is a minor DOC sink in temperate rivers.

     
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  3. Abstract

    Lakes are central components of the inland water system distinct from, yet inextricably connected to, river networks. Currently, existing network‐scale biogeochemistry research, although robust, typically treats each of these components separately or reductively. Here, we incorporate lake morphometry into a fully connected stream/lake network for the Connecticut River watershed and model potential evasion of terrestrially sourced headwater CO2as transported through the network, ignoring in‐stream production. We found that approximately 25%–30% of total potential soil CO2evasion occurs in lakes, and percent evasion is inversely related to streamflow. A lake's ability to evade CO2is controlled by residence time and size: most lakes with residence time over 7 days or surface area greater than 0.004 km2evade functionally all terrestrial CO2entering from upstream, precluding further downstream transport. We conclude that lakes are important for soil CO2degassing and that this coupled river/lake approach is promising for CO2studies henceforth.

     
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  4. Abstract

    Most terrestrial allochthonous organic matter enters river networks through headwater streams during high flow events. In headwaters, allochthonous inputs are substantial and variable, but become less important in streams and rivers with larger watersheds. As allochthonous dissolved organic matter (DOM) moves downstream, the proportion of less aromatic organic matter with autochthonous characteristics increases. How environmental factors converge to control this transformation of DOM at a continental scale is less certain. We hypothesized that the amount of time water has spent travelling through surface waters of inland systems (streams, rivers, lakes, and reservoirs) is correlated to DOM composition. To test this hypothesis, we used established river network scaling relationships to predict relative river network flow‐weighted travel time (FWTT) of water for 60 stream and river sites across the contiguous United States (3090 discrete samples over 10 water years). We estimated lentic contribution to travel times with upstream in‐network lake and reservoir volume. DOM composition was quantified using ultraviolet and visible absorption and fluorescence spectroscopy. A combination of FWTT and lake and reservoir volume was the best overall predictor of DOM composition among models that also incorporated discharge, specific discharge, watershed area, and upstream channel length. DOM spectral slope ratio (R2 = 0.77) and Freshness Index (R2 = 0.78) increased and specific ultraviolet absorbance at 254 nm (R2 = 0.68) and Humification Index (R2 = 0.44) decreased across sites as a function of FWTT and upstream lake volume. This indicates autochthonous‐like DOM becomes continually more dominant in waters with greater FWTT. We assert that river FWTT can be used as a metric of the continuum of DOM composition from headwaters to rivers. The nature of the changes to DOM composition detected suggest this continuum is driven by a combination of photo‐oxidation, biological processes, hydrologically varying terrestrial subsidies, and aged groundwater inputs.

     
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  5. Abstract

    At‐many‐stations hydraulic geometry (AMHG), while useful for estimating river discharge from satellite data, remains empirical and has yet to be reconciled with the at‐a‐station hydraulic geometry (AHG) from which it was originally derived. Here we present evidence, using United States Geological Survey field measurements of channel hydraulics for 155 rivers, that AMHG can be hydraulically and geomorphically reconciled with AHG. Our results indicate that AMHG is rightly understood as an expression of a river‐wide model of hydraulics driven by changes in slope imposed upon AHG physics. The explanatory power of AHG and this river‐wide model combine to determine whether AMHG exists: if both AHG and the river‐wide model adequately describe hydraulics, then we show that AMHG is a necessary mathematical consequence of these two phenomena. We also orient these findings in the context of river discharge estimation and other applications.

     
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  6. We investigated environmental, landscape, and microbial factors that could structure the spatiotemporal variability in the nontarget chemical composition of four riverine systems in the Oregon Coast Range, USA. We hypothesized that the nontarget chemical composition in river water would be structured by broad-scale landscape gradients in each watershed. Instead, only a weak relationship existed between the nontarget chemical composition and land cover gradients. Overall, the effects of microbial communities and environmental variables on chemical composition were nearly twice as large as those of the landscape, and much of the influence of environmental variables on the chemical composition was mediated through the microbial community (i.e., environment affects microbes, which affect chemicals). Therefore, we found little evidence to support our hypothesis that chemical spatiotemporal variability was related to broad-scale landscape gradients. Instead, we found qualitative and quantitative evidence to suggest that chemical spatiotemporal variability of these rivers is controlled by changes in microbial and seasonal hydrologic processes. While the contributions of discrete chemical sources are undeniable, water chemistry is undoubtedly impacted by broad-scale continuous sources. Our results suggest that diagnostic chemical signatures can be developed to monitor ecosystem processes, which are otherwise challenging or impossible to study with existing off-the-shelf sensors. 
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  7. The goods and services provided by riverine systems are critical to humanity, and our reliance increases with our growing population and demands. As our activities expand, these systems continue to degrade throughout the world even as we try to restore them, and many efforts have not met expectations. One way to increase restoration effectiveness could be to explicitly design restorations to promote microbial communities, which are responsible for much of the organic matter breakdown, nutrient removal or transformation, pollutant removal, and biomass production in river ecosystems. In this paper, we discuss several design concepts that purposefully create conditions for these various microbial goods and services, and allow microbes to act as ecological restoration engineers. Focusing on microbial diversity and function could improve restoration effectiveness and overall ecosystem resilience to the stressors that caused the need for the restoration. Advances in next-generation sequencing now allow the use of microbial ‘omics techniques (e.g., metagenomics, metatranscriptomics) to assess stream ecological conditions in similar fashion to fish and benthic macroinvertebrates. Using representative microbial communities from stream sediments, biofilms, and the water column may greatly advance assessment capabilities. Microbes can assess restorations and ecosystem function where animals may not currently be present, and thus may serve as diagnostics for the suitability of animal reintroductions. Emerging applications such as ecological metatranscriptomics may further advance our understanding of the roles of specific restoration designs towards ecological services as well as assess restoration effectiveness. 
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  8. Abstract Dissolved organic matter (DOM) impacts the structure and function of aquatic ecosystems. DOM absorbs light in the UV and visible (UV–Vis) wavelengths, thus impacting light attenuation. Because absorption by DOM depends on its composition, UV–Vis absorbance is used to constrain DOM composition, source, and amount. Ferric iron, Fe(III), also absorbs in the UV–Vis; when Fe(III) is present, DOM-attributed absorbance is overestimated. Here, we explore how differing behavior of DOM and Fe(III) at the catchment scale impacts UV–Vis absorbance and evaluate how system-specific variability impacts the effectiveness of existing Fe(III) correction factors in a temperate watershed. We sampled five sites in the Connecticut River mainstem bi-weekly for ~ 1.5 years, and seven sites in the Connecticut River watershed once during the summer 2019. We utilized size fractionation to isolate the impact of DOM and Fe(III) on absorbance and show that variable contributions of Fe(III) to absorbance at 254 nm (a 254 ) and 412 nm (a 412 ) by size fraction complicates correction for Fe(III). We demonstrate that the overestimation of DOM-attributed absorbance by Fe(III) is correlated to the Fe(III):dissolved organic carbon concentration ratio; thus, overestimation can be high even when Fe(III) is low. a 254 overestimation is highly variable even within a single system, but can be as high as 53%. Finally, we illustrate that UV-Vis overestimation might impart bias to seasonal, discharge, and land-use trends in DOM quality. Together, these findings argue that Fe(III) should be measured in tandem with UV–Vis absorbance for estimates of CDOM composition or amount. 
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  9. The magnitude of stream and river carbon dioxide (CO 2 ) emission is affected by seasonal changes in watershed biogeochemistry and hydrology. Global estimates of this flux are, however, uncertain, relying on calculated values for CO 2 and lacking spatial accuracy or seasonal variations critical for understanding macroecosystem controls of the flux. Here, we compiled 5,910 direct measurements of fluvial CO 2 partial pressure and modeled them against watershed properties to resolve reach-scale monthly variations of the flux. The direct measurements were then combined with seasonally resolved gas transfer velocity and river surface area estimates from a recent global hydrography dataset to constrain the flux at the monthly scale. Globally, fluvial CO 2 emission varies between 112 and 209 Tg of carbon per month. The monthly flux varies much more in Arctic and northern temperate rivers than in tropical and southern temperate rivers (coefficient of variation: 46 to 95 vs. 6 to 12%). Annual fluvial CO 2 emission to terrestrial gross primary production (GPP) ratio is highly variable across regions, ranging from negligible (<0.2%) to 18%. Nonlinear regressions suggest a saturating increase in GPP and a nonsaturating, steeper increase in fluvial CO 2 emission with discharge across regions, which leads to higher percentages of GPP being shunted into rivers for evasion in wetter regions. This highlights the importance of hydrology, in particular water throughput, in routing terrestrial carbon to the atmosphere via the global drainage networks. Our results suggest the need to account for the differential hydrological responses of terrestrial–atmospheric vs. fluvial–atmospheric carbon exchanges in plumbing the terrestrial carbon budget. 
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