Nitrate uptake across biomes and the influence of elemental stoichiometry: A new look at LINX II

Considering recent increases in anthropogenic N loading, it is essential to identify the controls on N removal and retention in aquatic ecosystems because the fate of N has consequences for water quality in streams and downstream ecosystems. Biological uptake of nitrate (NO3−) is a major pathway by which N is removed from these ecosystems. Here we used data from the second Lotic Intersite Nitrogen eXperiment (LINX II) in a multivariate analysis to identify the primary drivers of variation in NO3− uptake velocity among biomes. Across 69 study watersheds in North America, dissolved organic carbon:NO3− ratios and photosynthetically active radiation were identified as the two most important predictor variables in explaining NO3− uptake velocity. However, within a specific biome the predictor variables of NO3− uptake velocity varied and included various physical, chemical, and biological attributes. Our analysis demonstrates the broad control of elemental stoichiometry on NO3− uptake velocity as well as the importance of biome-specific predictors. Understanding this spatial variation has important implications for biome-specific watershed management and the downstream export of NO3−, as well as for development of spatially explicit global models that describe N dynamics in streams and rivers

Nitrate uptake enhanced by availability of dissolved organic matter in tropical montane streams

Tropical forests store large amounts of Earth’s terrestrial C, but many tropical montane streams have low dissolved organic matter (DOM). This low availability of energy likely limits certain pathways of inorganic N uptake, as evidenced by the high rates of nitrification and predominance of nitrate (NO3−) in the total pool of dissolved N seen in many tropical montane forests. To explore the influence of DOM availability on tropical stream N cycling, we performed nutrient pulse additions of NO3− with or without an added C source (acetate or urea) in streams of the Luquillo Experimental Forest, Puerto Rico. In the absence of added DOM, NO3− uptake was either undetectable or had very long (\u3e3000 m) uptake lengths (Sw). When DOM was added with NO3−, Sw values for NO3− were much shorter (97–1500 m), with the shortest lengths resulting from additions of acetate. Comparing uptake metrics of the added C sources, there was greater demand for acetate compared to urea, and measurable urea uptake was detected much less frequently. During NO3−-only additions, ambient concentrations of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) decreased in some cases, suggesting increased metabolic demand for energy from the ambient organic matter pool under elevated levels of inorganic nutrients. Collectively, these results demonstrate that pathways of inorganic N cycling are tightly tied to energy availability at this tropical site. The response of ambient DOC and DON to increases in NO3− concentrations points to important feedbacks between inorganic N and DOM including organic N. Understanding the controls on NO3− processing in these streams is important to predicting network-scale exports of N from tropical ecosystems

Leaf-litter leachate is distinct in optical properties and bioavailability to stream heterotrophs

Dissolved organic C (DOC) leached from leaf litter contributes to the C pool of stream ecosystems and affects C cycling in streams. We studied how differences in leaf-litter chemistry affect the optical properties and decomposition of DOC. We used 2 species of cottonwoods (Populus) and their naturally occurring hybrids that differ in leaf-litter phytochemistry and decomposition rate. We measured DOC and nutrient concentration in leaf leachates and determined the effect of DOC quality on heterotrophic respiration in 24-h incubations with stream sediments. Differences in DOC composition and quality were characterized with fluorescence spectroscopy. Rapidly decomposing leaves with lower tannin and lignin concentrations leached ~40 to 50% more DOC and total dissolved N than did slowly decomposing leaves. Rates of heterotrophic respiration were 25 to 50% higher on leachate from rapidly decomposing leaf types. Rates of heterotrophic respiration were related to metrics of aromaticity. Specifically, rates of respiration were correlated negatively with the Fluorescence Index and positively with Specific Ultraviolet Absorbance (SUVA254) and T280 tryptophan-like fluorescence peak. These results reveal that leaf-litter DOC is distinctly different from ambient streamwater DOC. The relationships between optical characteristics of leaf leachate and bioavailability are opposite those found in streamwater DOC. Differences in phytochemistry among leaf types can influence stream ecosystems with respect to DOC quantity, composition, and rates of stream respiration. These patterns suggest that the relationship between the chemical structure of DOC and its biogeochemistry is more complex than previously recognized. These unique properties of leaf-litter DOC will be important when assessing the effects of terrestrial C on aquatic ecosystems, especially during leaf fall

Wildfires lead to decreased carbon and increased nitrogen concentrations in upland arctic streams

The Central Siberian Plateau is undergoing rapid climate change that has resulted in increased frequency of forest fires and subsequent alteration of watershed carbon and nutrient dynamics. Across a watershed chronosequence (3 to \u3e100 years since wildfire) we quantified the effects of fire on quantity and composition of dissolved organic matter (DOM), stream water nutrient concentrations, as well as in-stream nutrient uptake. Wildfires increased concentrations of nitrate for a decade, while decreasing concentrations of dissolved organic carbon and nitrogen (DOC and DON) and aliphatic DOM contribution for five decades. These post-wildfire changes in stream DOM result in lower uptake efficiency of in-stream nitrate in recently burned watersheds. Nitrate uptake (as uptake velocity) is strongly dependent on DOM composition (e.g. polyphenolics), ambient dissolved inorganic nitrogen (DIN), and DOC to DIN ratios. Our observations and experiments suggest that a decade-long pulse of inorganic nitrogen and a reduction of DOC export occur following wildfires in streams draining the Central Siberian Plateau. Increased fire frequency in the region is thus likely to both decrease DOM and increase nitrate delivery to the main stem Yenisei River, and ultimately the Arctic Ocean, in the coming decades

Shifting stoichiometry: Long-term trends in stream-dissolved organic matter reveal altered C:N ratios due to history of atmospheric acid deposition

Este artículo contiene 17 páginas, 6 figuras, 2 tablas.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 energynutrient 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.National Institute of Food and Agriculture, Grant/Award Number: 1016163, 1019522 and 1022291; Natural Environment Research Council, Grant/Award Number: NE/K010689/1; NSF EPSCoR, Grant/ Award Number: EPS-1929148; Division of Environmental Biology, Grant/ Award Number: 1545288 and 1556603; European Regional Development Fund, Grant/Award Number: RTI2018-094521- B-100 and RYC-2017-22643Peer reviewe

Gradients of anthropogenic nutrient enrichment alter N Composition and DOM stoichiometry in freshwater ecosystems

Plain language summary Ammonium and nitrate in freshwaters have received considerable attention due to their clear ecological and health effects. A comprehensive assessment of N in freshwaters that includes DON is lacking. Including DON in studies of surface water chemistry is important because it can cause eutrophication and certain forms can be rapidly removed by microbial communities. Here, we document how elevated levels of TDN impact the concentrations and relative proportions of all three forms of dissolved N and the stoichiometry of DOM. Our results suggest that human activities fundamentally alter the composition of the dissolved nitrogen pool and the stoichiometry of DOM. Results also highlight feedbacks between the C and N cycles in freshwater ecosystems that are poorly studied.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

Priorities for synthesis research in ecology and environmental science

ACKNOWLEDGMENTS We thank the National Science Foundation grant #1940692 for financial support for this workshop, and the National Center for Ecological Analysis and Synthesis (NCEAS) and its staff for logistical support.Peer reviewedPublisher PD

Priorities for synthesis research in ecology and environmental science

ACKNOWLEDGMENTS We thank the National Science Foundation grant #1940692 for financial support for this workshop, and the National Center for Ecological Analysis and Synthesis (NCEAS) and its staff for logistical support.Peer reviewedPublisher PD

DOC:NO3− ratios and NO3− uptake in forested headwater streams

The underlying mechanisms driving the coupled interactions between inorganic nitrogen uptake and dissolved organic matter are not well understood, particularly in surface waters. To determine the relationship between dissolved organic carbon (DOC) quantity and nitrate (NO3−) uptake kinetics in streams, we performed a series of NO3− Tracer Additions for Spiraling Curve Characterization experiments in four streams within the Lamprey River Watershed, New Hampshire, across a range in background DOC concentrations (1–8 mg C/L). Experiments were performed throughout the 2013 and 2014 growing seasons. Across streams and experimental dates, ambient uptake velocity (Vf) correlated positively with increasing DOC concentrations and DOC:NO3− ratios but was only weakly negatively associated with NO3− concentrations. Ambient NO3− Vf was unrelated to pH, light, temperature, dissolved oxygen, and Specific Ultraviolet Absorbance at 254 nm. Although there were general tendencies across the entire Lamprey River Watershed, individual sites behaved differently in their uptake kinetics. NO3− uptake dynamics in the Lamprey River Watershed are most strongly influenced by DOC concentrations rather than NO3− concentrations or physicochemical parameters, which have been identified as regional- to continental-scale drivers in previous research. Understanding the fundamental relationships between dissolved organic matter and inorganic nutrients will be important as global and climatic changes influence the delivery and production of DOC and NO3− in aquatic ecosystems

Direct response of dissolved organic nitrogen to nitrate availability in headwater streams

Despite decades of research documenting the quantitative significance of dissolved organic nitrogen (DON) across ecosystems, the drivers controlling its production and consumption are not well understood. As an organic nutrient DON may serve as either an energy or nitrogen source. One hypothesized control on DON concentration in streams is nitrate (NO3−) availability. Synoptic surveys of DON and NO3−, however, have yielded inconsistent spatial and temporal patterns. Using a nutrient pulse method we experimentally manipulated stream NO3− and measured the response of both the manipulated solute and ambient concentrations of DON in three New Hampshire headwater streams. This direct experimental addition of NO3− often altered ambient DON concentrations in situ, with both increases and decreases observed. The overall relationship between NO3− and DON suggests that DON is primarily used as a nutrient source in these streams, as evidenced by net DON accumulation with added NO3−. However, strong underlying seasonal patterns in the response to NO3− addition are also discernable, indicating that the role of DON can switch between serving as a nutrient source to an energy source (as evidenced by net DON reduction with added NO3−). We also observed differences in the NO3−—DON relationship (net DON accumulation vs. net DON reduction) in two streams less than five miles apart when experiments were conducted within the same month. Based on these results, we expect the role of DON within ecosystems to vary among watersheds and throughout the growing season, alternating between serving as a nutrient and energy source depending on environmental conditions. With the incorporation of a new field-based method we demonstrate that the ambient DON pool can be manipulated in situ. This approach has the potential for furthering our understanding of DON across ecosystems