Storm events can drive highly variable behavior in catchment nutrient and water fluxes, yet short‐term event dynamics are frequently missed by low‐resolution sampling regimes. In addition, nutrient source zone contributions can vary significantly within and between storm events. Our inability to identify and characterize time‐dynamic source zone contributions severely hampers the adequate design of land use management practices in order to control nutrient exports from agricultural landscapes. Here we utilize an 8 month high‐frequency (hourly) time series of streamflow, nitrate (NO3‐N), dissolved organic carbon (DOC), and hydroclimatic variables for a headwater agricultural catchment. We identified 29 distinct storm events across the monitoring period. These events represented 31% of the time series and contributed disproportionately to nutrient loads (42% of NO3‐N and 43% of DOC) relative to their duration. Regression analysis identified a small subset of hydroclimatological variables (notably precipitation intensity and antecedent conditions) as key drivers of nutrient dynamics during storm events. Hysteresis analysis of nutrient concentration‐discharge relationships highlighted the dynamic activation of discrete NO3‐N and DOC source zones, which varied on an event‐specific basis. Our results highlight the benefits of high‐frequency in situ monitoring for characterizing short‐term nutrient fluxes and unraveling connections between hydroclimatological variability and river nutrient export and source zone activation under extreme flow conditions. These new process‐based insights, which we summarize in a conceptual model, are fundamental to underpinning targeted management measures to reduce nutrient loading of surface waters.

Greenhouse gas (GHG) emissions of carbon dioxide (CO2) and methane (CH4) from streambeds are currently understudied. There is a paucity of research exploring organic matter (OM) controls on GHG production by microbial metabolic activity in streambeds, which is a major knowledge gap given the increased inputs of allochthonous carbon to streams, especially in agricultural catchments. This study aims to contribute to closing this knowledge gap by quantifying how contrasting OM contents in different sediments affect streambed GHG production and associated microbial metabolic activity. We demonstrate, by means of an incubation experiment, that streambed sediments have the potential to produce substantial amounts of GHG, controlled by sediment OM quantity and quality. We observed streambed CO2 production rates that can account for 35% of total stream evasion estimated in previous studies, ranging between 1.4 and 86% under optimal conditions. Methane production varied stronger than CO2 between different geologic backgrounds, suggesting OM quality controls between streambed sediments. Moreover, our results indicate that streambed sediments may produce much more CO2 than quantified to date, depending on the quantity and quality of the organic matter, which has direct implications for global estimates of C fluxes in stream ecosystems.

Globally, rivers and streams are important sources of carbon dioxide and methane, with small rivers contributing disproportionately relative to their size. Previous research on greenhouse gas (GHG) emissions from surface water lacks mechanistic understanding of contributions from streambed sediments. We hypothesise that streambeds, as known biogeochemical hotspots, significantly contribute to the production of GHGs. With global climate change, there is a pressing need to understand how increasing streambed temperatures will affect current and future GHG production. Current global estimates assume linear relationships between temperature and GHG emissions from surface water. Here we show non-linearity and threshold responses of streambed GHG production to warming. We reveal that temperature sensitivity varies with substrate (of variable grain size), organic matter (OM) content and geological origin. Our results confirm that streambeds, with their non-linear response to projected warming, are integral to estimating freshwater ecosystem contributions to current and future global GHG emissions.

The use of multitracer field fluorometry is increasing in the hydrological sciences. However, obtaining high‐quality fluorescence measurements is challenging given the variability in environmental conditions within stream ecosystems. Here, we conducted a series of stream tracer tests to examine the degree to which multitracer field fluorometry produces reliable estimates of tracer concentrations under realistic field conditions. Using frequently applied examples of conservative (Uranine) and reactive (Resazurin‐Resorufin) fluorescent tracers, we show that in situ measurements of tracer breakthrough curves can deviate markedly from corresponding samples analyzed under laboratory conditions. To investigate the effects of key environmental variables on fluorescence measurements, we characterized the response of field fluorometer measurements to changes in temperature, turbidity, and tracer concentration. Results showed pronounced negative log‐linear effects of temperature on fluorescence measurements for all tracers, with stronger effects observed typically at lower tracer concentrations. We also observed linear effects of turbidity on fluorescence measurements that varied predictably with tracer concentration. Based on our findings, we present methods to correct field fluorometer measurements for variation in these parameters. Our results show how changing environmental conditions can introduce substantial uncertainties in the analysis of fluorescent tracer breakthrough curves, and highlight the importance of accounting for these changes to prevent incorrect inferences being drawn regarding the physical and biogeochemical processes underpinning observed patterns.

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