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  1. Abstract

    Headwater streams are control points for carbon dioxide (CO2) emissions to the atmosphere, with relative contributions to CO2emission fluxes from lateral groundwater inputs widely assumed to overwhelm those from in‐stream metabolic processes. We analyzed continuous measurements of stream dissolved CO2and oxygen (O2) concentrations during spring and early summer in two Mediterranean headwater streams from which we evaluated the contribution of in‐stream net ecosystem production (NEP) to CO2emission. The two streams exhibited contrasting hydrological regimes: one was non‐perennial with relatively small groundwater inflows, while the other was perennial and received significant lateral groundwater inputs. The non‐perennial stream exhibited strong inverse coupling between instantaneous and daily CO2and O2concentrations, and a strong correlation between aerobic ecosystem respiration (ER) and gross primary production (GPP) despite persistent negative NEP. At the perennial stream, the CO2–O2relationship varied largely over time, ER and GPP were uncorrelated, and NEP, which was consistently negative, increased with increasing temperature. Mean NEP contribution to CO2emission was 51% and 57% at the non‐perennial and perennial stream, respectively. Although these proportions varied with assumptions about metabolic stoichiometry and groundwater CO2concentration, in‐stream CO2production consistently and substantially contributed to total atmospheric CO2flux in both streams. We conclude that in‐stream metabolism can be more important for driving C cycling in some headwater streams than previously assumed.

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  2. Abstract

    Stream dissolved oxygen (DO) dynamics are an outcome of metabolic activity and subsequently regulate ecosystem functions such as in‐stream solute and sediment reactions. The synchronization of DO signals in and across stream networks is both a cause and effect of the mode and timing of these functions, but there is limited empirical evidence for network patterns of DO synchrony. We used high frequency DO measurements at 42 sites spanning five catchments and stream orders to evaluate DO signal synchrony in response to variation in light (a driver of photosynthesis) and discharge (a control on DO signal spatial extent). We hypothesized that stream network DO synchrony arises when regional controls dominate: when light inputs are synchronous and when longitudinal hydrologic connectivity is high. By complement, we predicted that DO signal synchrony decreases as light becomes more asynchronous and stream flows decline or become discontinuous. Our results supported this hypothesis: greater DO signal synchrony arose with increasing light synchrony and flow connectivity. A model including these two controls explained 70% of variation in DO synchrony. We conclude that DO synchrony patterns within‐ and across‐networks support the current paradigm of discharge and light control on stream metabolic activity. Finally, we propose that DO synchrony patterns are likely a useful prerequisite for scaling subdaily metabolism estimates to network and regional scales.

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  3. Abstract

    The Tracer Additions for Spiraling Curve Characterization (TASCC) model has been rapidly adopted to interpret in‐stream nutrient spiraling metrics over a range of concentrations from breakthrough curves (BTCs) obtained during pulse solute injection experiments. TASCC analyses often identify hysteresis in the relationship between spiraling metrics and concentration as nutrient concentration in BTCs rises and falls. The mechanisms behind these hysteresis patterns have yet to be determined. We hypothesized that differences in the time a solute is exposed to bioactive environments (i.e., biophysical opportunity) between the rising and falling limbs of BTCs causes hysteresis in TASCCs. We tested this hypothesis using nitrate data from Elkhorn Creek (CO, USA) combined with a process‐based particle‐tracking model representing travel times and transformations along each flow path in the water column and hyporheic zone, from which the bioactive zone comprised only a thin superficial layer. In‐stream nitrate uptake was controlled by hyporheic exchange and the cumulative time nitrate spend in the bioactive layer. This bioactive residence time generally increased from the rising to the falling limb of the BTC, systematically generating hysteresis in the TASCC curves. Hysteresis decreased when nutrient uptake primarily occurred in the water column compared to the hyporheic zone, and with increasing the distance between the injection and sampling points. Hysteresis increased with the depth of the hyporheic bioactive layer. Our results emphasize that good characterization of spatial heterogeneity of surface‐subsurface flow paths and bioactive hot spots within streams is essential to understanding the mechanisms of in‐stream nutrient uptake.

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  4. Abstract

    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.

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  5. Abstract

    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.

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