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IntroductionDissolved organic matter (DOM) composition varies over space and time, with a multitude of factors driving the presence or absence of each compound found in the complex DOM mixture. Compounds ubiquitously present across a wide range of river systems (hereafter termed core compounds) may differ in chemical composition and reactivity from compounds present in only a few settings (hereafter termed satellite compounds). Here, we investigated the spatial patterns in DOM molecular formulae presence (occupancy) in surface water and sediments across 97 river corridors at a continental scale using the “Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems—WHONDRS” research consortium. MethodsWe used a novel data-driven approach to identify core and satellite compounds and compared their molecular properties identified with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). ResultsWe found that core compounds clustered around intermediate hydrogen/carbon and oxygen/carbon ratios across both sediment and surface water samples, whereas the satellite compounds varied widely in their elemental composition. Within surface water samples, core compounds were dominated by lignin-like formulae, whereas protein-like formulae dominated the core pool in sediment samples. In contrast, satellite molecular formulae were more evenly distributed between compound classes in both sediment and water molecules. Core compounds found in both sediment and water exhibited lower molecular mass, lower oxidation state, and a higher degree of aromaticity, and were inferred to be more persistent than global satellite compounds. Higher putative biochemical transformations were found in core than satellite compounds, suggesting that the core pool was more processed. DiscussionThe observed differences in chemical properties of core and satellite compounds point to potential differences in their sources and contribution to DOM processing in river corridors. Overall, our work points to the potential of data-driven approaches separating rare and common compounds to reduce some of the complexity inherent in studying riverine DOM. 

Abstract Although time series in ecosystem metabolism are well characterized in small and medium rivers, patterns in the world's largest rivers are almost unknown. Large rivers present technical difficulties, including depth measurements, gas exchange (, ) estimates, and the presence of large dams, which can supersaturate gases. We estimated reach‐scale metabolism for the Hanford Reach of the Columbia River (Washington state, USA), a free‐flowing stretch with an average discharge of 3173 . We calculated from semi‐empirical models and directly estimated it from tracer measurements. We fixed at the median value from these calculations (0.5 ), and used maximum likelihood to estimate reach‐scale, open‐channel metabolism. Both gross primary production (GPP) and ecosystem respiration (ER) were high (GPP range: 0.3–30.8 g , ER range: 0.8–30.6 g ), with peak GPP and ER occurring in the late summer or early fall. GPP increased exponentially with temperature, consistent with metabolic theory, while light was seasonally saturating. Annual average GPP, estimated at 1500 g carbon , was in the top 2% of estimates for other rivers. GPP and ER were tightly coupled and 90% of GPP was immediately respired, resulting in net ecosystem production near 0. Patterns in the Hanford Reach contrast with those in small‐medium rivers, suggesting that metabolism magnitudes and patterns in large rivers may not be simply scaled from knowledge of smaller rivers. 

Abstract. A comprehensive set of measurements and calculated metricsdescribing physical, chemical, and biological conditions in the rivercorridor is presented. These data were collected in a catchment-wide,synoptic campaign in the H. J. Andrews ExperimentalForest (Cascade Mountains, Oregon, USA) in summer 2016 during low-dischargeconditions. Extensive characterization of 62 sites including surface water,hyporheic water, and streambed sediment was conducted spanning 1st- through5th-order reaches in the river network. The objective of the sample designand data acquisition was to generate a novel data set to support scaling ofriver corridor processes across varying flows and morphologic forms presentin a river network. The data are available at https://doi.org/10.4211/hs.f4484e0703f743c696c2e1f209abb842 (Ward, 2019). 

Abstract. Although most field and modeling studies of river corridorexchange have been conducted at scales ranging from tens to hundreds of meters,results of these studies are used to predict their ecological andhydrological influences at the scale of river networks. Further complicatingprediction, exchanges are expected to vary with hydrologic forcing and thelocal geomorphic setting. While we desire predictive power, we lack acomplete spatiotemporal relationship relating discharge to the variation ingeologic setting and hydrologic forcing that is expected across a riverbasin. Indeed, the conceptual model of Wondzell (2011) predicts systematicvariation in river corridor exchange as a function of (1) variation inbaseflow over time at a fixed location, (2) variation in discharge withlocation in the river network, and (3) local geomorphic setting. To testthis conceptual model we conducted more than 60 solute tracer studiesincluding a synoptic campaign in the 5th-order river network of the H. J. Andrews Experimental Forest (Oregon, USA) and replicate-in-time experimentsin four watersheds. We interpret the data using a series of metricsdescribing river corridor exchange and solute transport, testing forconsistent direction and magnitude of relationships relating these metricsto discharge and local geomorphic setting. We confirmed systematic decreasein river corridor exchange space through the river networks, from headwatersto the larger main stem. However, we did not find systematic variation withchanges in discharge through time or with local geomorphic setting. Whileinterpretation of our results is complicated by problems with the analyticalmethods, the results are sufficiently robust for us to conclude that space-for-timeand time-for-space substitutions are not appropriate in our study system.Finally, we suggest two strategies that will improve the interpretability oftracer test results and help the hyporheic community develop robust datasets that will enable comparisons across multiple sites and/or dischargeconditions. 

Abstract Fluvial networks integrate, transform, and transport constituents from terrestrial and aquatic ecosystems. To date, most research on water quality dynamics has focused on process understanding at individual streams, and, as a result, there is a lack of studies analyzing how physical and biogeochemical drivers scale across fluvial networks. We performed tracer tests in five stream orders of the Jemez River continuum in New Mexico, USA, to quantify reach‐scale hyporheic exchange during two different seasonal periods to address the following: How do hyporheic zone contributions to overall riverine processing change with space and time? And does the spatiotemporal variability of hyporheic exchange scale across fluvial networks? Combining conservative (i.e., bromide) and reactive (i.e., resazurin) tracer analyses with solute transport modeling, we found a dominance of reaction‐limited transport conditions and a decrease of the contributions of hyporheic processing across stream orders and flow regimes. Our field‐based findings suggest that achieving knowledge transferability of hyporheic processing within fluvial networks may be possible, especially when process variability is sampled across multiple stream orders and flow regimes. Therefore, we propose a shift in our traditional approach to investigating scaling patterns in transport processes, which currently relies on the interpretation of studies conducted in multiple sites (mainly in headwater streams) that are located in different fluvial networks, to a more cohesive, network‐centered investigation of processes using the same or readily comparable methods.