Stream Nitrate Responds Rapidly to Decreasing Nitrate Deposition

Ecosystem acidification and eutrophication resulting from increased deposition of dissolved inorganic nitrogen (DIN) are issues of increasing global concern. Consequently, costly policy decisions are being implemented to decrease nitrogen oxide (NO _x ) emissions. Although declining DIN deposition along with rapid declines of DIN in surface waters have been reported in parts of Europe, the same observation is just emerging in North America. Here we find a significant decline in bulk deposition NO₃ ⁻ during the later part of a 28-year record in southcentral Ontario, Canada. Despite high N retention and substantial inter-annual variability in the long-term record due to periods of drought, we find significant declines in annual NO₃ ⁻ concentrations and export at six out of 11 streams that drain upland-dominated catchments. In contrast, five streams draining primarily wetland-dominated catchments with lower levels of NO₃ ⁻ show no decreasing trend in NO₃ ⁻ concentration or export. The rapid response in stream NO₃ ⁻ to declining atmospheric inputs was observed at sites with historically moderate inputs of DIN (~870 mg m⁻² y⁻¹) in bulk deposition. Topographic features such as slope, and related catchment features including wetland cover, appear to influence which catchments will respond positively to declining DIN deposition. These findings force us to revise our original conceptualization of the N saturation status of these catchments.     

Seasonal Variations of Dissolved Nitrogen and DOC:DON Ratios in an Intermittent Mediterranean Stream

Seasonal variations of dissolved inorganic nitrogen (DIN) (NO₃–N and NH₄–N) and dissolved organic nitrogen (DON) were determined in Fuirosos, an intermittent stream draining an unpolluted Mediterranean forested catchment (10.5 km²) in Catalonia (Spain). The influence of flow on streamwater concentrations and seasonal differences in quality and origin of dissolved organic matter, inferred from dissolved organic carbon to nitrogen ratios (DOC:DON ratios), were examined. During baseflow conditions, nitrate and ammonium had opposite behaviour, probably controlled by biological processes such as vegetation uptake and mineralization activity. DON concentrations did not have a seasonal trend. During storms, nitrate and DON increased by several times but discharge was not a good predictor of nutrient concentrations. DOC:DON ratios in streamwater were around 26, except during the months following drought when DOC:DON ratios ranged between 42 and 20 during baseflow and stormflow conditions, respectively. Annual N export during 2000–2001 was 70 kg km⁻¹ year⁻¹, of which 75% was delivered during stormflow. The relative contribution of nitrogen forms to the total annual export was 57, 35 and 8% as NO₃–N, DON and NH₄–N, respectively.     

Factors Controlling Sediment Denitrification in Midwestern Streams of Varying Land Use

We investigated controls on stream sediment denitrification in nine headwater streams in the Kalamazoo River Watershed, Michigan, USA. Factors influencing denitrification were determined by using experimental assays based on the chloramphenicol-amended acetylene inhibition technique. Using a coring technique, we found that sediment denitrification was highest in the top 5 cm of the benthos and was positively related to sediment organic content. To determine the effect of overlying water quality on sediment denitrification, first-order stream sediments were assayed with water from second- and third-order downstream reaches, and often showed higher denitrification rates relative to assays using site-specific water from the first-order stream reach. Denitrification was positively related to nitrate (NO₃ ⁻) concentration, suggesting that sediments may have been nutrient-limited. Using stream-incubated inorganic substrata of varying size classes, we found that finer-grained sand showed higher rates of denitrification compared to large pebbles, likely due to increased surface area per volume of substratum. Denitrification was measurable on both inorganic substrata and fine particulate organic matter loosely associated with inorganic particles, and denitrification rates were related to organic content. Using nutrient-amended denitrification assays, we found that sediment denitrification was limited by NO₃ ⁻ or dissolved organic carbon (DOC, as dextrose) variably throughout the year. The frequency and type of limitation differed with land use in the watershed: forested streams were NO₃ ⁻-limited or co-limited by both NO₃ ⁻ and DOC 92% of the time, urban streams were more often NO₃ ⁻-limited than DOC-limited, whereas agricultural stream sediments were DOC-limited or co-limited but not frequently limited by NO₃ ⁻ alone.     

Controls on soil nitrification and stream nitrate export at two forested catchments

Dormant season inorganic nitrogen (N) leaching varies considerably among forested catchments with similar bedrock, forest cover and deposition history. Recent work has highlighted the importance of winter rain-on-snow (ROS) events as a source of winter nitrate (NO₃-N) export, but differences among streams are likely due to differences in baseflow NO₃-N concentrations, and thus soil N processes. The objective of this study was to investigate rates of N-mineralization and nitrification as well as their potential environmental controls throughout the year, but with particular focus on the winter season in south-central Ontario, Canada. Field incubations were utilized to assess differences in NO₃-N and ammonium production over time and across topographic positions in two catchments with contrasting patterns of N export. Rates of nitrification were similar to rates of total mineralization, and nitrification rates were significantly higher during the summer and spring compared with the winter and fall; however, winter nitrification was substantial, and ranged from 19 to 36 % of annual rates. Seasonal differences in nitrification were largely driven by temperature, soil moisture and inorganic N concentration in soil. Rain and melting snow infiltrated the soil during ROS events, which were associated with increased NO₃-N availability, particularly in well-drained soils, and ROS-induced increases in stream nitrate concentrations were largest at the catchment dominated by well-drained soil. Annual nitrification fluxes were almost two orders of magnitude greater than N deposition or NO₃-N leaching fluxes at either catchment. Similar rates of NO₃-N production within the two catchments suggest that consumption of NO₃-N within wet soils is responsible for the 10-fold difference in NO₃-N export between the two streams. Notably, these results suggest that consumption processes were important for reducing NO₃-N export even during winter ROS events.     

The effects of dissolved organic carbon,acidity and seasonality on metal geochemistry within a forested catchment on the Precambrian Shield,central Ontario,Canada

Metal pollution, in combination with other environmental stressors such as acid deposition and climate change, may disturb metal biogeochemical cycles. To investigate the influence of dissolved organic carbon, acidity and seasonality on metal geochemistry, this study has described concentrations of 19 metals as they pass through an acidified forested catchment on the Precambrian Shield in south-central Ontario, Canada. Metal, dissolved organic carbon (DOC) and sulphate (SO₄ ²⁻) concentrations fluctuate throughout the catchment compartments as the water passes through and interacts with vegetation, soils and bedrock. Relationships among metals, DOC and SO₄ ²⁻ are most pronounced in compartments where DOC and SO₄ ²⁻ exhibit high variability, namely in the throughfall, organic horizon soil water, and wetland-draining stream. Metal, DOC and SO₄ ²⁻ concentrations varied seasonally in the streams, and temporal coherence occurred among metal, DOC and SO₄ ²⁻ concentrations in the organic horizon soil water and the wetland-draining stream (PC1). In the wetland-draining stream, the highest DOC, Cr, Cu, Fe, Pb, and V concentrations occur in the summer, whereas concentrations of SO₄ ²⁻ and most other metals peak in the fall after a period of drought. Despite the rural location, provincial water quality objectives for surface water were exceeded for many metals when the peak fall values occurred.     

Biogeochemical Budgets in a Mediterranean Catchment with High Rates of Atmospheric N Deposition – Importance of Scale and Temporal Asynchrony

In this study biogeochemical export in a set of catchments that vary from 6 ha to almost 1500 ha is investigated. Studying catchments across this large range of scales enables us to investigate the scale dependence and fundamental processes controlling catchment biogeochemical export that would not have been possible with a more limited data set. The Devil Canyon catchment, in the San Bernardino Mountains, California, has some of the highest atmospheric N deposition rates in the world (40–90 kg ha⁻¹year⁻¹ at the crest of the catchment). These high rates of deposition have translated into consistently high levels of NO⁻in 3 some streams of the San Bernardino Mountains. However, the streams of the Devil Canyon catchment have widely varying dissolved inorganic nitrogen (DIN) concentrations and export. These differences are also, to a more limited extent, present for dissolved organic carbon (DOC) but not in other dissolved species (Cl⁻, SO²⁻₄,Ca²⁺ and other weathering products). As catchment size increases DIN and DOC concentrations first increase until catchment area is ∼150 ha but then decrease as catchment scale increases beyond that size. The scale dependence of DIN export implies that catchments at different spatial scales are at different degrees of N saturation. The reason for this scale effect appears to be the dominance of flushing of DIN out of soil at small scales due to the temporal asynchrony between nutrient availability and biological N demand, the groundwater exfiltration of this flushed DIN at intermediate scales and the removal of this DIN from streamflow through in-stream processes and groundwater–surface water interaction at larger scales. While the particular scale effect observed here may not occur over the same range in catchment area in other ecosystems, it is likely that other ecosystems have similar scale dependant export for DIN and DOC.     

Riparian control on NO3 −, DOC, and dissolved Fe concentrations in mountainous streams, northern Japan

We evaluated (1) the longitudinal pattern of stream chemistry and (2) the effects of the riparian zone on this longitudinal pattern for nitrate (NO₃ ⁻), dissolved organic carbon (DOC), and total dissolved iron (Fe). We selected two small watersheds; the “southern watershed” had an extending riparian wetland and the “northern watershed” had a narrow riparian area. Stream NO₃ ⁻ concentrations decreased from the spring to outlet of both watersheds. In the southern watershed, stream DOC concentration decreased from the spring to midstream and then increased to the outlet. Stream Fe concentration in the southern watershed longitudinally increased. On the other hand, the northern watershed exhibited no longitudinal pattern for DOC and Fe concentrations. In both watersheds, while NO₃ ⁻ concentrations in the soil and ground water were lower than those in the stream waters, DOC and Fe concentrations exhibited the opposite patterns. The longitudinal decreases of NO₃ ⁻ concentrations in both streams and increase of stream Fe in the southern watershed mainly resulted from the inflow of the soil and ground water to the stream. The decrease in stream DOC from the spring to midstream in the southern watershed was due to the deep groundwater having low DOC, while the subsequent increase to the surrounding soil and ground water. Moreover, considerations of stream solute flow with soil and ground water chemistry suggested other mechanisms adding NO₃ ⁻ and removing/diluting DOC and Fe, especially for the northern watershed; coexistence of oxidizing and reducing conditions in the riparian zone might control the longitudinal concentration change in the stream water chemistry.     

Dissolved organic carbon and nitrate concentrations in streams: a useful index indicating carbon and nitrogen availability in catchments

Dissolved organic carbon (DOC) and NO₃^– are important forms of C and N in stream water. Hypotheses concerning relationships between DOC and NO₃^– concentrations have been proposed, but there are no reports demonstrating a relationship between them in stream water. We observed 35 natural streams in the Lake Biwa watershed, central Japan, and found an inverse relationship between DOC and NO₃^– concentrations. This relationship was also found in observations of their seasonal variations in the Lake Biwa watershed. Moreover, this relationship was also found to apply to watersheds in other regions in Japan. These results suggest that forest biogeochemical processes which control DOC and NO₃^– concentrations in Japanese streams are closely related. Excess N availability together with a C (energy) deficit in a soil environment may explain this relationship. DOC and NO₃^– concentrations in streams will thus be a useful index indicating C and N availability in catchments.     

Hydrological and biological processes modulate carbon,nitrogen and phosphorus flux from the St. Lawrence River to its estuary (Quebec,Canada)

Changes in atmospheric deposition, stream water chemistry, and solute fluxes were assessed across 15 small forested catchments. Dramatic changes in atmospheric deposition have occurred over the last three decades, including a 70% reduction in sulphur (S) deposition. These changes in atmospheric inputs have been associated with expected changes in levels of acidity, sulphate and base cations in streams. Soil retention of S appeared to partially explain rates of chemical recovery. In addition to these changes in acid–base chemistry we also observed unexpected changes in nitrogen (N) biogeochemistry and nutrient stoichiometry of stream water, including decreased stream N concentrations. Among all catchments the average flux of dissolved inorganic nitrogen (DIN) was best predicted by average runoff, soil chemistry (forest floor C/N) and levels of acid deposition (both S and N). The rate of change in stream DIN flux, however, was much more closely correlated with reductions in rates of S deposition rather than those of DIN. Unlike DIN fluxes, the average concentrations as well as the rates of decline in streamwater nitrate (NO₃) concentration over time were tightly linked to stream dissolved organic carbon/dissolved organic nitrogen ratios DOC/DON and DON/TP rather than catchment characteristics. Declines in phosphorus adsorption with increasing soil pH appear to contribute to the relationship between C, N, and P in our study catchments. Our observations suggest that catchment P availability and its alteration due to environmental changes (e.g. acidification) might have profound effects on N cycling and catchment N retention that have been largely unrecognized.     

Landscape Controls on Organic and Inorganic Nitrogen Leaching across an Alpine/Subalpine Ecotone,Green Lakes Valley,Colorado Front Range

Here we report measurements of organic and inorganic nitrogen (N) fluxes from the high-elevation Green Lakes Valley catchment in the Colorado Front Range for two snowmelt seasons (1998 and 1999). Surface water and soil samples were collected along an elevational gradient extending from the lightly vegetated alpine to the forested subalpine to assess how changes in land cover and basin area affect yields and concentrations of ammonium-N (NH₄-N), nitrate-N (NO₃-N), dissolved organic N (DON), and particulate organic N (PON). Streamwater yields of NO₃-N decreased downstream from 4.3 kg ha⁻¹ in the alpine to 0.75 kg ha⁻¹ at treeline, while yields of DON were much less variable (0.40–0.34 kg ha⁻¹). Yields of NH₄-N and PON were low and showed little variation with basin area. NO₃-N accounted for 40%–90% of total N along the sample transect and was the dominant form of N at all but the lowest elevation site. Concentrations of DON ranged from approximately 10% of total N in the alpine to 45% in the subalpine. For all sites, volume-weighted mean concentrations of total dissolved nitrogen (TDN) were significantly related to the DIN:DON ratio (R ² = 0.81, P < 0.001) Concentrations of NO₃-N were significantly higher at forested sites that received streamflow from the lightly vegetated alpine reaches of the catchment than in a control catchment that was entirely subalpine forest, suggesting that the alpine may subsidize downstream forested systems with inorganic N. KCl-extractable inorganic N and microbial biomass N showed no relationship to changes in soil properties and vegetative cover moving downstream in catchment. In contrast, soil carbon–nitrogen (C:N) ratios increased with increasing vegetative cover in catchment and were significantly higher in the subalpine compared to the alpine (P < 0.0001) Soil C:N ratios along the sample transect explained 78% of the variation in dissolved organic carbon (DOC) concentrations and 70% of the variation in DON concentrations. These findings suggest that DON is an important vector for N loss in high-elevation ecosystems and that streamwater losses of DON are at least partially dependent on catchment soil organic matter stoichiometry. Received 26 July 2001; accepted 6 May 2002.     

Stormflow Dynamics of Dissolved Organic Carbon and Total Dissolved Nitrogen in a Small Urban Watershed

We examined patterns of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) loading to a small urban stream during baseflow and stormflow. We hypothesized that lower DOC and TDN contributions from impervious surfaces would dilute natural hydrologic flowpath (i.e., riparian) contributions during storm events in an urban watershed, resulting in lower concentrations of DOC and TDN during storms. We tested these hypotheses in a small urban watershed in Portland, Oregon, over a 3-month period during the spring of 2003. We compared baseflow and stormflow chemistry using Mann–Whitney tests (significant at p<0.05). We also applied a mass balance to the stream to compare the relative significance of impervious surface contributions versus riparian contributions of DOC and TDN. Results showed a significant increase in stream DOC concentrations during stormflows (median baseflow DOC = 2.00 mg l⁻¹ vs. median stormflow DOC = 3.46 mg l⁻¹). TDN streamwater concentrations, however, significantly decreased with stormflow (median baseflow TDN = 0.75 mg l⁻¹ vs. median stormflow TDN = 0.56 mg l⁻¹). During storms, remnant riparian areas contributed 70–74% of DOC export and 38–35% of TDN export to the stream. The observed pattern of increased DOC concentrations during stormflows in this urban watershed was similar to patterns found in previous studies of forested watersheds. Results for TDN indicated that there were relatively high baseflow nitrogen concentrations in the lower watershed that may have partially masked the remnant riparian signal during stormflows. Remnant riparian areas were a major source of DOC and TDN to the stream during storms. These results suggest the importance of preserving near-stream riparian areas in cities to maintain ambient carbon and nitrogen source contributions to urban streams.     

Unusual seasonal patterns and inferred processes of nitrogen retention in forested headwaters of the Upper Susquehanna River

Atmospheric deposition contributes a large fraction of the annual nitrogen (N) input to the basin of the Susquehanna River, a river that provides two-thirds of the annual N load to the Chesapeake Bay. Yet, there are few measurements of the retention of atmospheric N in the Upper Susquehanna’s forested headwaters. We characterized the amount, form (nitrate, ammonium, and dissolved organic nitrogen), isotopic composition (δ¹⁵N- and δ¹⁸O-nitrate), and seasonality of stream N over 2 years for 7–13 catchments. We expected high rates of N retention and seasonal nitrate patterns typical of other seasonally snow-covered catchments: dormant season maxima and growing season minima. Coarse estimates of N export indicated high rates of inorganic N retention (>95%), yet streams had unexpected seasonal nitrate patterns, with summer peaks (14–96 μmol L⁻¹), October crashes (<1 μmol L⁻¹), and modest rebounds during the dormant season (<1–20 μmol L⁻¹). Stream δ¹⁸O-nitrate values indicated microbial nitrification as the primary source of stream nitrate, although snowmelt or other atmospheric source contributed up to 47% of stream nitrate in some March samples. The autumn nitrate crash coincided with leaffall, likely due to in-stream heterotrophic uptake of N. Hypothesized sources of the summer nitrate peaks include: delayed release of nitrate previously flushed to groundwater, weathering of geologic N, and summer increases in net nitrate production. Measurements of shale δ¹⁵N and soil-, well-, and streamwater nitrate within one catchment point toward a summer increase in soil net nitrification as the driver of this pattern. Rather than seasonal plant demand, processes governing the seasonal production, retention, and transport of nitrate in soils may drive nitrate seasonality in this and many other systems.     

Dissolved Nitrogen, Phosphorus, and Sulfur forms in the Ecosystem Fluxes of a Montane Forest in Ecuador

The N, P, and S cycles in pristine forests are assumed to differ from those of anthropogenically impacted areas, but there are only a few studies to support this. Our objective was therefore to assess the controls of N, P, and S release, immobilization, and transport in a remote tropical montane forest. The study forest is located on steep slopes of the northern Andes in Ecuador. We determined the concentrations of NO₃-N, NH₄-N, dissolved organic N (DON), PO₄-P, dissolved organic P (DOP), SO₄-S, dissolved organic S (DOS), and dissolved organic C (DOC) in rainfall, throughfall, stemflow, lateral flow (in the organic layer), litter leachate, mineral soil solution, and stream water of three 8–13 ha catchments (1900–2200 m a.s.l.). The organic forms of N, P, and S contributed, on average, 55, 66, and 63% to the total N, P, and S concentrations in all ecosystem fluxes, respectively. The organic layer was the largest source of all N, P, and S species except for inorganic P and S. Most PO₄ was released in the canopy by leaching and most SO₄ in the mineral soil by weathering. The mineral soil was a sink for all studied compounds except for SO₄. Consequently, concentrations of dissolved inorganic and organic N and P were as low in stream water (TDN: 0.34–0.39 mg N l⁻¹, P not detectable) as in rainfall (TDN: 0.39–0.48 mg N l⁻¹, P not detectable), whereas total S concentrations were elevated (stream water: 0.04–0.15, rainfall: 0.01–0.07 mg S l⁻¹). Dissolved N, P, and S forms were positively correlated with pH at the scale of soil peda except inorganic S. Soil drying and rewetting promoted the release of dissolved inorganic N. High discharge levels following heavy rainstorms were associated with increased DOC, DON, NO₃-N and partly also NH₄-N concentrations in stream water. Nitrate-N concentrations in the stream water were positively correlated with stream discharge during the wetter period of the year. Our results demonstrate that the sources and sinks of N, P, and S were element-specific. More than half of the cycling N, P, and S was organic. Soil pH and moisture were important controls of N, P, and S solubility at the scale of individual soil peda whereas the flow regime influenced the export with stream water.     

DOC and DIC in Flowpaths of Amazonian Headwater Catchments with Hydrologically Contrasting Soils

Organic and inorganic carbon (C) fluxes transported by water were evaluated for dominant hydrologic flowpaths on two adjacent headwater catchments in the Brazilian Amazon with distinct soils and hydrologic responses from September 2003 through April 2005. The Ultisol-dominated catchment produced 30% greater volume of storm-related quickflow (overland flow and shallow subsurface flow) compared to the Oxisol-dominated catchment. Quickflow fluxes were equivalent to 3.2 ± 0.2% of event precipitation for the Ultisol catchment, compared to 2.5 ± 0.3% for the Oxisol-dominated watershed (mean response ±1 SE, n = 27 storms for each watershed). Hydrologic responses were also faster on the Ultisol watershed, with time to peak flow occurring 10 min earlier on average as compared to the runoff response on the Oxisol watershed. These different hydrologic responses are attributed primarily to large differences in saturated hydraulic conductivity (K _s). Overland flow was found to be an important feature on both watersheds. This was evidenced by the response rates of overland flow detectors (OFDs) during the rainy season, with overland flow intercepted by 54 ± 0.5% and 65 ± 0.5% of OFDs for the Oxisol and Ultisol watersheds respectively during biweekly periods. Small volumes of quickflow correspond to large fluxes of dissolved organic C (DOC); DOC concentrations of the hydrologic flowpaths that comprise quickflow are an order of magnitude higher than groundwater flowpaths fueling base flow (19.6 ± 1.7 mg l⁻¹ DOC for overland flow and 8.8 ± 0.7 mg l⁻¹ DOC for shallow subsurface flow versus 0.50 ± 0.04,mg l⁻¹ DOC in emergent groundwater). Concentrations of dissolved inorganic C (DIC, as dissolved CO₂–C plus HCO₃⁻–C) in groundwater were found to be an order of magnitude greater than quickflow DIC concentrations (21.5 mg l⁻¹ DIC in emergent groundwater versus 1.1 mg l⁻¹ DIC in overland flow). The importance of deeper flowpaths in the transport of inorganic C to streams is indicated by the 40:1 ratio of DIC:DOC for emergent groundwater. Dissolved CO₂–C represented 92% of DIC in emergent groundwater. Results from this study illustrate a highly dynamic and tightly coupled linkage between the C cycle and the hydrologic cycle for both Ultisol and Oxisol landscapes: organic C fluxes strongly tied to flowpaths associated with quickflow, and inorganic C (particularly dissolved CO₂) transported via deeper flowpaths.     

Nitrogen retention in the riparian zone of catchments underlain by discontinuous permafrost

1. Riparian zones function as important ecotones that reduce nitrate concentration in groundwater and inputs into streams. In the boreal forest of interior Alaska, permafrost confines subsurface flow through the riparian zone to shallow organic horizons, where plant uptake of nitrate and denitrification are typically high. 2. In this study, riparian zone nitrogen retention was examined in a high permafrost catchment (approximately 53% of land area underlain by permafrost) and a low permafrost catchment (approximately 3%). To estimate the contribution of the riparian zone to catchment nitrogen retention, we analysed groundwater chemistry using an end‐member mixing model. 3. Stream nitrate concentration was over twofold greater in the low permafrost catchment than the high permafrost catchment. Riparian groundwater was not significantly different between catchments, averaging 13 μm overall. Nitrogen retention, measured using the end‐member mixing model, averaged 0.75 and 0.22 mmol N m^?2 day^?1 in low and high permafrost catchments, respectively, over the summer. The retention rate of nitrogen in the riparian zone was 10–15% of the export in stream flow. 4. Our results indicate that the riparian zone functions as an important sink for groundwater nitrate and dissolved organic carbon (DOC). However, differences in stream nitrate and DOC concentrations between catchments cannot be explained by solute inputs from riparian groundwater to the stream and differences between streams are probably attributable to deeper groundwater inputs or flows from springs that bypass the riparian zone.     

Thaw depth determines reaction and transport of inorganic nitrogen in valley bottom 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.     

High Nitrate Retention during Winter in Soils of the Hubbard Brook Experimental Forest

Stream export of nitrogen (N) as nitrate (NO₃⁻; the most mobile form of N) from forest ecosystems is thought to be controlled largely by plant uptake of inorganic N, such that reduced demand for plant N during the non-growing season and following disturbances results in increased stream NO₃⁻ export. The roles of microbes and soils in ecosystem N retention are less clear, but are the dominant controls on N export when plant uptake is low. We used a mass balance approach to investigate soil N retention during winter (December through March) at the Hubbard Brook Experimental Forest by comparing NO₃⁻ inputs (atmospheric deposition), internal production (soil microbial nitrification), and stream output. We focused on months when plant N uptake is nearly zero and the potential for N export is high. Although winter months accounted for only 10–15% of annual net nitrification, soil NO₃⁻ production (0.8–1.0 g N m⁻² winter⁻¹) was much greater than stream export (0.03–0.19 N m⁻² winter⁻¹). Soil NO₃⁻ retention in two consecutive winters was high (96% of combined NO₃⁻ deposition and soil production; year 1) even following severe plant disturbance caused by an ice-storm (84%; year 2) We show that soil NO₃⁻ retention is surprisingly high even when N demand by plants is low. Our study highlights the need to better understand mechanisms of N retention during the non-growing season to predict how ecosystems will respond to high inputs of atmospheric N, disturbance, and climate change.     

Dual isotope analyses indicate efficient processing of atmospheric nitrate by forested watersheds in the northeastern U.S.

Nitrogen from atmospheric deposition serves as the dominant source of new nitrogen to forested ecosystems in the northeastern U.S. By combining isotopic data obtained using the denitrifier method, with chemical and hydrologic measurements we determined the relative importance of sources and control mechanisms on nitrate (NO₃ ⁻) export from five forested watersheds in the Connecticut River watershed. Microbially produced NO₃ ⁻ was the dominant source (82–100%) of NO₃ ⁻ to the sampled streams as indicated by the δ¹⁵N and δ¹⁸O of NO₃ ⁻. Seasonal variations in the δ¹⁸O–NO₃ ⁻ in streamwater are controlled by shifting hydrologic and temperature affects on biotic processing, resulting in a relative increase in unprocessed NO₃ ⁻ export during winter months. Mass balance estimates find that the unprocessed atmospherically derived NO₃ ⁻ stream flux represents less than 3% of the atmospherically delivered wet NO₃ ⁻ flux to the region. This suggests that despite chronically elevated nitrogen deposition these forests are not nitrogen saturated and are retaining, removing, and reprocessing the vast majority of NO₃ ⁻ delivered to them throughout the year. These results confirm previous work within Northeastern U.S. forests and extend observations to watersheds not dominated by a snow-melt driven hydrology. In contrast to previous work, unprocessed atmospherically derived NO₃ ⁻ export is associated with the period of high recharge and low biotic activity as opposed to spring snowmelt and other large runoff events.     

Influence of land use on stream ecosystem function in a Mediterranean catchment

1. Due to the hierarchical organization of stream networks, land use changes occurring at larger spatial scales (i.e. the catchment) can affect physical, chemical and biological characteristics at lower spatial scales, ultimately altering stream structure and function. Anthropogenic effects on streams have primarily been documented using structural metrics such as water chemistry, channel alteration and algal biomass. Functional parameters, including metrics of nutrient retention and metabolism, are now being widely used as indicators of stream condition. 2. Within this hierarchical context, we used a multivariate approach to examine how structural and functional (i.e. nutrient retention and metabolism) attributes of streams are related to catchment variables, including land use. The study was done in 13 streams located within a single Mediterranean catchment, but draining sub‐catchments with contrasting land use. 3. At the catchment scale, results showed two contrasting land use gradients: (i) from forested‐ to urban‐dominated catchments and (ii) from low to moderate agricultural‐dominated catchments. Variation in structural and functional parameters was strongly related to these land use gradients. Specifically, NH₄⁺ demand (measured as the uptake velocity, V_f) decreased along the gradient from forested‐ to urban‐dominated catchments primarily in response to increases in stream nutrient concentrations [NH₄⁺, dissolved organic nitrogen (DON) and carbon (DOC)]. Both primary production and respiration increased along the gradient of agricultural development in response to increases in algal biomass (chlorophyll a). Soluble reactive phosphorus demand was not related to any of the land use gradients. 4. Our results illustrate the connections among factors operating at different spatial scales (i.e. from catchments to streams) and their distinct influence on stream ecosystem function. Managers should take into consideration these connections when designing stream management and restoration plans. Because ecologically successful stream management and restoration is expected to restore function as well as structure to streams, the use of appropriate measures of functional processes is required. Nutrient retention and metabolism parameters are good candidates to fill this gap.     

Concentration and composition of dissolved organic carbon in streams in relation to catchment soil properties

Two adjacent catchments in the Otway Ranges of Victoria, Australia (Redwater and Clearwater) produce water with markedly different concentrations of dissolved organic carbon (DOC) during summer. Water from Redwater Creek had a DOC concentration of 32 mg L^–1, while water from Clearwater Creek had a DOC concentration of 3.8 mg L^–1. Examination of the catchments revealed that while climate, topography, vegetation and land use were similar, the soils were different. The objective of this study was to examine the relationship between the concentration and chemical composition of DOC in stream waters and the nature of soils in the two catchments. Soil mapping determined that clayey soils formed on Cretaceous sediments (Cretaceous soils) occurred throughout both catchments, but that Redwater Catchment also contained a large area (39%) of sandy soils formed on Tertiary sediments (Tertiary soils). The concentration of DOC in forest floor leachate was high in both the Tertiary and Cretaceous areas; however, the concentration of DOC in water draining areas dominated by Tertiary soils was greater than that in water draining areas dominated by Cretaceous soils. Laboratory experiments showed that the Cretaceous soils had higher adsorption capacities for forest floor leachate DOC than the Tertiary soils. The difference in DOC concentrations of the streams was therefore attributed to the difference in adsorption capacity of catchment soils for DOC. Adsorption capacities of the soils were found to be a function of their clay contents and specific surface areas.Solid-state³C nuclear magnetic resonance spectroscopy and pyrolysis-mass spectrometry were used to determine the chemical structure of DOC found in streams and forest floor leachate samples and that remaining in solution after interaction with soil. Chemistry of DOC in forest floor leachate was similar before and after interaction with soil, indicating no preferential adsorption of a particular type of carbon. Thus, differences between the chemical structure of stream DOC and forest floor leachate DOC could be attributed to microbial modifications during its movement through soils and into the streams, rather than losses by adsorption.