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Processes that drive variability in catchment solute sourcing, transformation, and transport can be investigated using concentration–discharge (C–Q) relationships. These relationships reflect catchment and in‐stream processes operating across nested temporal scales, incorporating both short and long‐term patterns. Scientists can therefore leverage catchment‐scale C–Q datasets to identify and distinguish among the underlying meteorological, biological, and geological processes that drive solute export patterns from catchments and influence the shape of their respective C–Q relationships. We have synthesized current knowledge regarding the influence of biological, geological, and meteorological processes on C–Q patterns for various solute types across diel to decadal time scales. We identify cross‐scale linkages and tools researchers can use to explore these interactions across time scales. Finally, we identify knowledge gaps in our understanding of C–Q temporal dynamics as reflections of catchment and in‐stream processes. We also lay the foundation for developing an integrated approach to investigate cross‐scale linkages in the temporal dynamics of C–Q relationships, reflecting catchment biogeochemical processes and the effects of environmental change on water quality.

This article is categorized under:

Science of Water > Hydrological Processes

Freshwater ecosystems reflect the landscapes in which they are embedded. The biogeochemistry of these systems is fundamentally linked to climate and watershed processes that control fluxes of water and the mobilization of energy and nutrients imprinting as variation in stream water chemistry. Disentangling these processes is difficult as they operate at multiple scales varying across space. We examined the relative importance of climate, soil, and watershed characteristics in mediating direct and indirect pathways that influence carbon and nitrogen availability in streams and rivers across spatial scales. Our data set comprised landscape and climatic variables and 37,995 chemistry measurements of carbon and nitrogen across 459 streams and rivers spanning the continental United States. Models explained a small fraction of carbon and nitrogen concentrations at the continental scale (25% and 6%, respectively) but 61% and 40%, respectively, at smaller spatial scales. Hydrometeorological processes were always important in mediating the availability of solutes but the mechanistic implications were variable across spatial scales. The influence of hydrometeorology on concentrations was often not direct, rather it was mediated by soil characteristics for carbon and watershed characteristics for nitrogen. For example, the seasonality of precipitation was often important in determining carbon concentrations through its influence on soil moisture at biogeoclimatic spatial scales, whereas it had a direct influence on concentrations at the continental scale. Our results suggest that hydrometeorological forcing remains the consistent driver of energy and nutrient concentrations but the mechanism influencing patterns varies across broad spatial scales.

Riverine exports of silicon (Si) influence global carbon cycling through the growth of marine diatoms, which account for ∼25% of global primary production. Climate change will likely alter river Si exports in biome‐specific ways due to interacting shifts in chemical weathering rates, hydrologic connectivity, and metabolic processes in aquatic and terrestrial systems. Nonetheless, factors driving long‐term changes in Si exports remain unexplored at local, regional, and global scales. We evaluated how concentrations and yields of dissolved Si (DSi) changed over the last several decades of rapid climate warming using long‐term data sets from 60 rivers and streams spanning the globe (e.g., Antarctic, tropical, temperate, boreal, alpine, Arctic systems). We show that widespread changes in river DSi concentration and yield have occurred, with the most substantial shifts occurring in alpine and polar regions. The magnitude and direction of trends varied within and among biomes, were most strongly associated with differences in land cover, and were often independent of changes in river discharge. These findings indicate that there are likely diverse mechanisms driving change in river Si biogeochemistry that span the land‐water interface, which may include glacial melt, changes in terrestrial vegetation, and river productivity. Finally, trends were often stronger in months outside of the growing season, particularly in temperate and boreal systems, demonstrating a potentially important role of shifting seasonality for the flux of Si from rivers. Our results have implications for the timing and magnitude of silica processing in rivers and its delivery to global oceans.

We examined how climate variability affects the mobilization of material from six watersheds. We analyzed one to seven years of high‐frequency sensor data from a temperate ecosystem and a tropical rainforest. We applied a windowed analysis to correlate concentration‐discharge (C‐Q) behavior with climate anomalies, providing insight into how hydrological and biogeochemical processes change in response to climate variability. Positive precipitation anomalies homogenized the C‐Q responses for dissolved organic matter, nitrate, specific conductance and turbidity, indicating that hydrological processes dominate the C‐Q signal and watersheds act as “conveyor belts” of material. In contrast, drier and warmer conditions led to C‐Q behavior associated with variation in solute concentration, suggesting that biogeochemical processes are a primary control on solute export and their response to flow. Results indicate that climate variability can move watersheds along a continuum from transporter‐to‐transformer of biologically active solutes and responses can potentially vary by biome.

Catchments in the Luquillo Experimental Forest (LEF) of Puerto Rico are warm, wet and tropical with steep elevational relief creating gradients in temperature and rainfall. Long‐term objectives of research at the site are to understand how changing climate and disturbance regimes alter hydrological and biogeochemical processes in the montane tropics and to provide information critical for managing and conserving tropical forest ecosystems globally. Measurements of hydrology and meteorology span decades, and currently include temperature, humidity, precipitation, cloud base level, throughfall, groundwater table elevation and stream discharge. The chemistry of rain, throughfall, and streams is measured weekly and lysimeters and wells are sampled monthly to quarterly. Multiple data sets document the effects of major hurricanes including Hugo (1989), Georges (1998) and Maria (2017) on vegetation, biota and catchment biogeochemistry and provide some of the longest available records of biogeochemical fluxes in tropical forests. Here we present an overview of the findings and the data sets that have been generated from the LEF, highlighting their importance for understanding montane tropical watersheds in the context of disturbance and global environmental change.

Dissolved organic carbon (DOC) and nitrogen (DON) are important energy and nutrient sources for aquatic ecosystems. In many northern temperate, freshwater systems DOC has increased in the past 50 years. Less is known about how changes in DOC may vary across latitudes, and whether changes in DON track those of DOC. Here, we present long‐term DOC and DON data from 74 streams distributed across seven sites in biomes ranging from the tropics to northern boreal forests with varying histories of atmospheric acid deposition. For each stream, we examined the temporal trends of DOC and DON concentrations and DOC:DON molar ratios. While some sites displayed consistent positive or negative trends in stream DOC and DON concentrations, changes in direction or magnitude were inconsistent at regional or local scales. DON trends did not always track those of DOC, though DOC:DON ratios increased over time for ~30% of streams. Our results indicate that the dissolved organic matter (DOM) pool is experiencing fundamental changes due to the recovery from atmospheric acid deposition. Changes in DOC:DON stoichiometry point to a shifting energy‐nutrient balance in many aquatic ecosystems. Sustained changes in the character of DOM can have major implications for stream metabolism, biogeochemical processes, food webs, and drinking water quality (including disinfection by‐products). Understanding regional and global variation in DOC and DON concentrations is important for developing realistic models and watershed management protocols to effectively target mitigation efforts aimed at bringing DOM flux and nutrient enrichment under control.

A comprehensive cross‐biome assessment of major nitrogen (N) species that includes dissolved organic N (DON) is central to understanding interactions between inorganic nutrients and organic matter in running waters. Here, we synthesize stream water N chemistry across biomes and find that the composition of the dissolved N pool shifts from highly heterogeneous to primarily comprised of inorganic N, in tandem with dissolved organic matter (DOM) becoming more N‐rich, in response to nutrient enrichment from human disturbances. We identify two critical thresholds of total dissolved N (TDN) concentrations where the proportions of organic and inorganic N shift. With low TDN concentrations (0–1.3 mg/L N), the dominant form of N is highly variable, and DON ranges from 0% to 100% of TDN. At TDN concentrations above 2.8 mg/L, inorganic N dominates the N pool and DON rarely exceeds 25% of TDN. This transition to inorganic N dominance coincides with a shift in the stoichiometry of the DOM pool, where DOM becomes progressively enriched in N and DON concentrations are less tightly associated with concentrations of dissolved organic carbon (DOC). This shift in DOM stoichiometry (defined as DOC:DON ratios) suggests that fundamental changes in the biogeochemical cycles of C and N in freshwater ecosystems are occurring across the globe as human activity alters inorganic N and DOM sources and availability. Alterations to DOM stoichiometry are likely to have important implications for both the fate of DOM and its role as a source of N as it is transported downstream to the coastal ocean.

River corridors integrate the active channels, geomorphic floodplain and riparian areas, and hyporheic zone while receiving inputs from the uplands and groundwater and exchanging mass and energy with the atmosphere. Here, we trace the development of the contemporary understanding of river corridors from the perspectives of geomorphology, hydrology, ecology, and biogeochemistry. We then summarize contemporary models of the river corridor along multiple axes including dimensions of space and time, disturbance regimes, connectivity, hydrochemical exchange flows, and legacy effects of humans. We explore how river corridor science can be advanced with a critical zone framework by moving beyond a primary focus on discharge-based controls toward multi-factor models that identify dominant processes and thresholds that make predictions that serve society. We then identify opportunities to investigate relationships between large-scale spatial gradients and local-scale processes, embrace that riverine processes are temporally variable and interacting, acknowledge that river corridor processes and services do not respect disciplinary boundaries and increasingly need integrated multidisciplinary investigations, and explicitly integrate humans and their management actions as part of the river corridor. We intend our review to stimulate cross-disciplinary research while recognizing that river corridors occupy a unique position on the Earth's surface.