Understanding links between water-quality variables and nitrate concentration in freshwater streams using high frequency sensor data.

Real-time monitoring using in-situ sensors is becoming a common approach for measuring water-quality within watersheds. High-frequency measurements produce big datasets that present opportunities to conduct new analyses for improved understanding of water-quality dynamics and more effective management of rivers and streams. Of primary importance is enhancing knowledge of the relationships between nitrate, one of the most reactive forms of inorganic nitrogen in the aquatic environment, and other water-quality variables. We analysed high-frequency water-quality data from in-situ sensors deployed in three sites from different watersheds and climate zones within the National Ecological Observatory Network, USA. We used generalised additive mixed models to explain the nonlinear relationships at each site between nitrate concentration and conductivity, turbidity, dissolved oxygen, water temperature, and elevation. Temporal auto-correlation was modelled with an auto-regressive-moving-average (ARIMA) model and we examined the relative importance of the explanatory variables. Total deviance explained by the models was high for all sites (99%). Although variable importance and the smooth regression parameters differed among sites, the models explaining the most variation in nitrate contained the same explanatory variables. This study demonstrates that building a model for nitrate using the same set of explanatory water-quality variables is achievable, even for sites with vastly different environmental and climatic characteristics. Applying such models will assist managers to select cost-effective water-quality variables to monitor when the goals are to gain a spatial and temporal in-depth understanding of nitrate dynamics and adapt management plans accordingly.

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

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.

Reconstructing Missing and Anomalous Data Collected from High-Frequency In-Situ Sensors in Fresh Waters.

In situ sensors that collect high-frequency data are used increasingly to monitor aquatic environments. These sensors are prone to technical errors, resulting in unrecorded observations and/or anomalous values that are subsequently removed and create gaps in time series data. We present a framework based on generalized additive and auto-regressive models to recover these missing data. To mimic sporadically missing (i) single observations and (ii) periods of contiguous observations, we randomly removed (i) point data and (ii) day- and week-long sequences of data from a two-year time series of nitrate concentration data collected from Arikaree River, USA, where synoptically collected water temperature, turbidity, conductance, elevation, and dissolved oxygen data were available. In 72% of cases with missing point data, predicted values were within the sensor precision interval of the original value, although predictive ability declined when sequences of missing data occurred. Precision also depended on the availability of other water quality covariates. When covariates were available, even a sudden, event-based peak in nitrate concentration was reconstructed well. By providing a promising method for accurate prediction of missing data, the utility and confidence in summary statistics and statistical trends will increase, thereby assisting the effective monitoring and management of fresh waters and other at-risk ecosystems.

River ecosystem conceptual models and non-perennial rivers: A critical review.

Conceptual models underpin river ecosystem research. However, current models focus on continuously flowing rivers and few explicitly address characteristics such as flow cessation and drying. The applicability of existing conceptual models to nonperennial rivers that cease to flow (intermittent rivers and ephemeral streams, IRES) has not been evaluated. We reviewed 18 models, finding that they collectively describe main drivers of biogeochemical and ecological patterns and processes longitudinally (upstream-downstream), laterally (channel-riparian-floodplain), vertically (surface water-groundwater), and temporally across local and landscape scales. However, perennial rivers are longitudinally continuous while IRES are longitudinally discontinuous. Whereas perennial rivers have bidirectional lateral connections between aquatic and terrestrial ecosystems, in IRES, this connection is unidirectional for much of the time, from terrestrial-to-aquatic only. Vertical connectivity between surface and subsurface water occurs bidirectionally and is temporally consistent in perennial rivers. However, in IRES, this exchange is temporally variable, and can become unidirectional during drying or rewetting phases. Finally, drying adds another dimension of flow variation to be considered across temporal and spatial scales in IRES, much as flooding is considered as a temporally and spatially dynamic process in perennial rivers. Here, we focus on ways in which existing models could be modified to accommodate drying as a fundamental process that can alter these patterns and processes across spatial and temporal dimensions in streams. This perspective is needed to support river science and management in our era of rapid global change, including increasing duration, frequency, and occurrence of drying.

Experimental nitrogen and phosphorus enrichment stimulates multiple trophic levels of algal and detrital-based food webs: a global meta-analysis from streams and rivers.

Anthropogenic increases in nitrogen (N) and phosphorus (P) concentrations can strongly influence the structure and function of ecosystems. Even though lotic ecosystems receive cumulative inputs of nutrients applied to and deposited on land, no comprehensive assessment has quantified nutrient-enrichment effects within streams and rivers. We conducted a meta-analysis of published studies that experimentally increased concentrations of N and/or P in streams and rivers to examine how enrichment alters ecosystem structure (state: primary producer and consumer biomass and abundance) and function (rate: primary production, leaf breakdown rates, metabolism) at multiple trophic levels (primary producer, microbial heterotroph, primary and secondary consumers, and integrated ecosystem). Our synthesis included 184 studies, 885 experiments, and 3497 biotic responses to nutrient enrichment. We documented widespread increases in organismal biomass and abundance (mean response = +48%) and rates of ecosystem processes (+54%) to enrichment across multiple trophic levels, with no large differences in responses among trophic levels or between autotrophic or heterotrophic food-web pathways. Responses to nutrient enrichment varied with the nutrient added (N, P, or both) depending on rate versus state variable and experiment type, and were greater in flume and whole-stream experiments than in experiments using nutrient-diffusing substrata. Generally, nutrient-enrichment effects also increased with water temperature and light, and decreased under elevated ambient concentrations of inorganic N and/or P. Overall, increased concentrations of N and/or P altered multiple food-web pathways and trophic levels in lotic ecosystems. Our results indicate that preservation or restoration of biodiversity and ecosystem functions of streams and rivers requires management of nutrient inputs and consideration of multiple trophic pathways.

Permafrost collapse alters soil carbon stocks, respiration, CH4 , and N2O in upland tundra.

Release of greenhouse gases from thawing permafrost is potentially the largest terrestrial feedback to climate change and one of the most likely to occur; however, estimates of its strength vary by a factor of thirty. Some of this uncertainty stems from abrupt thaw processes known as thermokarst (permafrost collapse due to ground ice melt), which alter controls on carbon and nitrogen cycling and expose organic matter from meters below the surface. Thermokarst may affect 20-50% of tundra uplands by the end of the century; however, little is known about the effect of different thermokarst morphologies on carbon and nitrogen release. We measured soil organic matter displacement, ecosystem respiration, and soil gas concentrations at 26 upland thermokarst features on the North Slope of Alaska. Features included the three most common upland thermokarst morphologies: active-layer detachment slides, thermo-erosion gullies, and retrogressive thaw slumps. We found that thermokarst morphology interacted with landscape parameters to determine both the initial displacement of organic matter and subsequent carbon and nitrogen cycling. The large proportion of ecosystem carbon exported off-site by slumps and slides resulted in decreased ecosystem respiration postfailure, while gullies removed a smaller portion of ecosystem carbon but strongly increased respiration and N2 O concentration. Elevated N2 O in gully soils persisted through most of the growing season, indicating sustained nitrification and denitrification in disturbed soils, representing a potential noncarbon permafrost climate feedback. While upland thermokarst formation did not substantially alter redox conditions within features, it redistributed organic matter into both oxic and anoxic environments. Across morphologies, residual organic matter cover, and predisturbance respiration explained 83% of the variation in respiration response. Consistent differences between upland thermokarst types may contribute to the incorporation of this nonlinear process into projections of carbon and nitrogen release from degrading permafrost.

Thaw depth determines reaction and transport of inorganic nitrogen in valley bottom permafrost soils: Nitrogen cycling in permafrost soils.

Nitrate (NO3 (-) ) export coupled with high inorganic nitrogen (N) concentrations in Alaskan streams suggests that N cycles of permafrost-influenced ecosystems are more open than expected for N-limited ecosystems. We tested the hypothesis that soil thaw depth governs inorganic N retention and removal in soils due to vertical patterns in the dominant N transformation pathways. Using an in situ, push-pull method, we estimated rates of inorganic N uptake and denitrification during snow melt, summer, and autumn, as depth of soil-stream flowpaths increased in the valley bottom of an arctic and a boreal catchment. Net NO3 (-) uptake declined sharply from snow melt to summer and decreased as a nonlinear function of thaw depth. Peak denitrification rate occurred during snow melt at the arctic site, in summer at the boreal site, and declined as a nonlinear function of thaw depth across both sites. Seasonal patterns in ammonium (NH4 (+) ) uptake were not significant, but low rates during the peak growing season suggest uptake that is balanced by mineralization. Despite rapid rates of hydrologic transport during snow melt runoff, rates of uptake and removal of inorganic N tended to exceed water residence time during snow melt, indicating potential for retention of N in valley bottom soils when flowpaths are shallow. Decreased reaction rates relative to water residence time in subsequent seasons suggest greater export of inorganic N as the soil-stream flowpath deepens due to thawing soils. Using seasonal thaw as a proxy for longer term deepening of the thaw layer caused by climate warming and permafrost degradation, these results suggest increasing potential for export of inorganic N from permafrost-influenced soils to streams.

Successional and physical controls on the retention of nitrogen in an undisturbed boreal forest ecosystem.

Floristic succession in the boreal forest can have a dramatic influence on ecosystem nutrient cycling. We predicted that a decrease in plant and microbial demand for nitrogen (N) during the transition from mid- to late-succession forests would induce an increase in the leaching of dissolved inorganic nitrogen (DIN), relative to dissolved organic nitrogen (DON). To test this, we examined the chemistry of the soil solution collected from within and below the main rooting zones of mid- and late-succession forests, located along the Tanana River in interior Alaska. We also used a combination of hydrological and chemical analyses to investigate a key assumption of our methodology: that patterns of soil water movement did not change during this transition. Between stands, there was no difference in the proportion of DIN below the rooting zone. 84-98% of DIN at both depths consisted of nitrate, which was significantly higher in the deeper mineral soil than at the soil surface (0.46+/-0.12 mg NO(-) (3) -N l(-1) vs 0.17+/-0.12 mg NO(-) (3) -N l(-1), respectively), and 79-92% of the total dissolved N consisted of DON. Contrary to our original assumption that nutrients were primarily leached downward, out of the rooting zone, we found much evidence to suggest that the glacially-fed Tanana River (>200 m from these stands) was contributing to the influx of water and nutrients into the soil active layer of both stands. Soil water potentials were positively correlated with river discharge; and ionic and isotopic (delta(18)O of H(2)O) values of the soil solution closely matched those of river water. Thus, our ability to elucidate biological control over ecosystem N retention was confounded by riverine nutrient inputs. Climatic warming is likely to extend the season of glacial melt and increase riverine nutrient inputs to forests along glacially-fed rivers.

An overview of the descent and landing of the Huygens probe on Titan.

Titan, Saturn's largest moon, is the only Solar System planetary body other than Earth with a thick nitrogen atmosphere. The Voyager spacecraft confirmed that methane was the second-most abundant atmospheric constituent in Titan's atmosphere, and revealed a rich organic chemistry, but its cameras could not see through the thick organic haze. After a seven-year interplanetary journey on board the Cassini orbiter, the Huygens probe was released on 25 December 2004. It reached the upper layer of Titan's atmosphere on 14 January and landed softly after a parachute descent of almost 2.5 hours. Here we report an overview of the Huygens mission, which enabled studies of the atmosphere and surface, including in situ sampling of the organic chemistry, and revealed an Earth-like landscape. The probe descended over the boundary between a bright icy terrain eroded by fluvial activity--probably due to methane-and a darker area that looked like a river- or lake-bed. Post-landing images showed centimetre-sized surface details.