Organic matter (OM) metabolism in freshwater ecosystems is a critical source of uncertainty in global biogeochemical cycles, yet aquatic OM cycling remains poorly understood. Here, we present the first work to explicitly test OM thermodynamics as a key regulator of aerobic respiration, challenging long-held beliefs that organic carbon and oxygen concentrations are the primary determinants of respiration rates. We pair controlled microcosm experiments with ultrahigh-resolution OM characterization to demonstrate a clear relationship between OM thermodynamic favorability and aerobic respiration under carbon limitation. We also demonstrate a shift in the regulation of aerobic respiration from OM thermodynamics to nitrogen content when carbon is in excess, highlighting a central role for OM thermodynamics in aquatic biogeochemical cycling particularly in carbon-limited ecosystems. Our work therefore illuminates a structural gap in aquatic biogeochemical models and presents a new paradigm in which OM thermodynamics and nitrogen content interactively govern aerobic respiration.. CC-BY-NC-ND 4.0 International license available under a (which was not certified by peer review) is the author/funder, who has granted bioRxiv a license to display the preprint in perpetuity. It is made Metabolism of organic matter (OM) in freshwater ecosystems plays a large role in global biogeochemical cycles 1-3 , as freshwater ecosystems emit more than 2 Pg C yr -1 into the atmosphere 4,5 . These emissions are largely dominated by contributions from river corridors 1,5,6 , and within the river corridor, areas of groundwater-surface water mixing (hyporheic zones) have a disproportionate impact on aerobic respiration [7][8][9] . Recent field observations have suggested that OM chemistry, and in particular OM thermodynamics, are key to predicting aerobic respiration in hyporheic zones [10][11][12] . If supported, these observations challenge a widespread paradigm that organic carbon and oxygen concentrations are the primary determinants of aerobic respiration rates and highlight a key source of model uncertainty. Yet, no work has provided direct evidence for OM thermodynamics as a regulator of aerobic respiration in a controlled laboratory environment. Demonstrating this behavior would identify mechanisms that drive field-based phenomena and would enable key properties of OM to be represented in predictive models, thereby contributing to reducing the uncertainty in modeling river corridor biogeochemical cycling 13,14 . microbiome composition or gene expression, corresponds to elevated biogeochemical function in the hyporheic zone.

River corridor metabolomes reflect organic matter (OM) processing that drives aquatic biogeochemical cycles. Recent work highlights the power of ultrahigh-resolution mass spectrometry for understanding metabolome composition and river corridor metabolism. However, there have been no studies on the global chemogeography of surface water and sediment metabolomes using ultrahigh-resolution techniques. Here, we describe a community science effort from the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium to characterize global metabolomes in surface water and sediment that span multiple stream orders and biomes. We describe the distribution of key aspects of metabolomes including elemental groups, chemical classes, indices, and inferred biochemical transformations. We show that metabolomes significantly differ across surface water and sediment and that surface water metabolomes are more rich and variable. We also use inferred biochemical transformations to identify core metabolic processes shared among surface water and sediment. Finally, we observe significant spatial variation in sediment metabolites between rivers in the eastern and western portions of the contiguous United States. Our work not only provides a basis for understanding global patterns in river corridor biogeochemical cycles but also demonstrates that community science endeavors can enable global research projects that are unfeasible with traditional research models.

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Abstract. Although most field and modeling studies of river corridor exchange have been conducted a scales ranging from 10’s to 100’s of meters; results of these studies are used to predict their ecological and hydrological influences at the scale of river networks. Further complicating prediction, exchange are expected to vary with hydrologic forcing and the local geomorphic setting. While we desire predictive power, we lack a complete spatiotemporal relationship relating discharge to the variation in geologic setting and hydrologic forcing that are expected across a river basin. Indeed, Wondzell’s [2011] conceptual model predicts systematic variation in river corridor exchange as a function of (1) variation in discharge over time at a fixed location, (2) variation in discharge with location in the river network, and (3) local geomorphic setting. To test this conceptual model we conducted more than 60 solute tracer studies collected in a synoptic campaign in the 5th order river network of the H. J. Andrews Experimental Forest (Oregon, USA). We interpret the data using a series of metrics describing river corridor exchange and solute transport, testing for consistent direction and magnitude of relationships relating these metrics to discharge and local geomorphic setting. We confirmed systematic decrease in river corridor exchange space through the river networks, from headwaters to the larger mainstem. However, we did not find systematic variation with changes in discharge through time, nor with local geomorphic setting. While interpretation of our results are complicated by problems with the analytical methods, they are sufficiently robust for us to conclude that space-for-time and time-for-space substitutions are not appropriate in our study system. Finally, we suggest two strategies that will improve the interpretability of tracer test results and help the hyporheic community develop robust data sets that will enable comparisons across multiple sites and/or discharge conditions.

Abstract. Although most field and modeling studies of river corridor exchange have been conducted at scales ranging from tens to hundreds of meters, results of these studies are used to predict their ecological and hydrological influences at the scale of river networks. Further complicating prediction, exchanges are expected to vary with hydrologic forcing and the local geomorphic setting. While we desire predictive power, we lack a complete spatiotemporal relationship relating discharge to the variation in geologic setting and hydrologic forcing that is expected across a river basin. Indeed, the conceptual model of Wondzell (2011) predicts systematic variation in river corridor exchange as a function of (1) variation in baseflow over time at a fixed location, (2) variation in discharge with location in the river network, and (3) local geomorphic setting. To test this conceptual model we conducted more than 60 solute tracer studies including a synoptic campaign in the 5th-order river network of the H. J. Andrews Experimental Forest (Oregon, USA) and replicate-in-time experiments in four watersheds. We interpret the data using a series of metrics describing river corridor exchange and solute transport, testing for consistent direction and magnitude of relationships relating these metrics to discharge and local geomorphic setting. We confirmed systematic decrease in river corridor exchange space through the river networks, from headwaters to the larger main stem. However, we did not find systematic variation with changes in discharge through time or with local geomorphic setting. While interpretation of our results is complicated by problems with the analytical methods, the results are sufficiently robust for us to conclude that space-for-time and time-for-space substitutions are not appropriate in our study system. Finally, we suggest two strategies that will improve the interpretability of tracer test results and help the hyporheic community develop robust datasets that will enable comparisons across multiple sites and/or discharge conditions.