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Most of eastern North America receives elevated levels of atmospheric deposition of sulfur (S) that result from anthropogenic SO2 emissions from fossil fuel combustion. Atmospheric S deposi- tion has acidified sensitive terrestrial and aquatic ecosystems in this region; however, deposition has been declining since the 1970s, resulting in some recovery in previously acidified aquatic ecosystems. Accurate watershed S mass balances help to evaluate the extent to which atmospheric S deposition is retained within ecosystems, and whether internal cycling sources and biogeochemical processes may be affecting the rate of recovery from decreasing S atmospheric loads. This study evaluated S mass balances for 15 sites with watersheds in southeastern Canada and northeastern US for the period 1985 to 2002. These 15 sites included nine in Canada (Turkey

We estimated net anthropogenic phosphorus inputs (NAPI) to 18 Lake Michigan (LM) and 6 Lake Erie (LE) watersheds for 1974, 1978, 1982, 1987, and 1992. NAPI quantifies all anthropogenic inputs of P (fertilizer use, atmospheric deposition, and detergents) as well as trade of P in food and feed, which can be a net input or output. Fertilizer was the dominant input overall, varying by three orders of magnitude among the 24 watersheds, but detergent was the largest input in the most urbanized watershed. NAPI increased in relation to area of disturbed land (R2 = 0.90) and decreased with forested and wetland area (R2 = 0.90). Export of P by rivers varied with NAPI, especially for the 18 watersheds of LM (R2 = 0.93), whereas the relationship was more variable among the six LE watersheds (R2 = 0.59). On average, rivers of the LE watersheds exported about 10% of NAPI, whereas LM watersheds exported 5% of estimated NAPI. A comparison of our results with others as well as nitrogen (N) budgets suggests that fractional export of P may vary regionally, as has been reported for N, and the proportion of P inputs exported by rivers appears lower than comparable findings with N.

We performed a meta-data analysis to investigate the importance of event based fluxes to DOC export from forested watersheds. A total of 30 small eastern United States forested watersheds with no wetland component, with a total of 5,176 DOC and accompanying discharge measurements were used in this analysis. There is a clear increase in DOC concentration during hydrologic events (storms and snow melt) that follows a power relationship. We estimate that 86% of DOC is exported during events. The majority (70%) of this event based DOC flux occurs during the rising hydrograph and during large events. Events with a discharge greater than 1.38 cm day−1 make up only 4.8% of the annual hydrograph, yet are responsible for 57% of annual DOC flux. The relationship between event discharge and both DOC concentration and flux is also regulated by temperature and antecedent conditions, with a larger response in both fluxes and concentrations to events during warmer periods and periods where the preceding discharge was low. The temperature relationship also shows seasonality indicating a potential link to the size or reactivity of watershed OM pools. The 86% of DOC lost during events represents a conservative estimate of the amount of allochthonous forested DOC transported laterally to streams. Future research on watershed cycling of DOC should take into account the importance of events in regulating the transport of DOC to downstream ecosystems, determine the relative importance of abiotic versus biotic processes for the temperature regulation of event-associated DOC fluxes, and elucidate the interactions between processes that respond to climate on event versus longer time scales.

Many ecologists and biogeochemists explore the interaction of the nitrogen (N) and phosphorus (P) cycles by addressing N:P ratios. While N:P ratios are recognized as broadly important to the composition and functioning of lotic ecosystems, the fundamental controls on stream water N:P ratio variation remains poorly understood. Low N:P ratio (less than 16) streams appear more likely in arid climates than in mesic climates, suggesting possible hydrologic or landscape controls. We explored the importance of watershed hydrology to the variation of total N to total P (TN:TP) ratios in stream water, and whether such variation is characteristically different across watershed classes based on mean annual precipitation and median observed TN:TP ratio. Nonparametric scatter plot analysis was applied to normalized TN:TP ratios and associated discharge (Q) measurements from 57 minimally-impacted watersheds from the contiguous United States. At the seasonal scale, TN:TP ratios showed a negative relationship with Q in semiarid climates and a positive relationship with Q in humid climates. Over storm event scales, TN:TP ratios decline with increasing Q across all watershed classes. The results broadly indicate hydrology is an important driver of TN:TP ratio variation over multiple time scales. We hypothesize that the broad differences across watershed classes are driven by variation in the nature of connectivity (frequency and magnitude of connections) of the landscape to streams. A strong physical control of N:P ratios in stream water is in stark contrast to the biological control of N:P ratios in the oceans, suggesting that application of stoichiometric theory—developed using marine systems—to lotic systems requires a broader consideration of controlling factors.

Seasonal and diurnal variations of in-stream NO3-N concentration oscillations were studied through high-frequency measurements of streamwater’s physical, chemical parameters (in-stream NO3-N concentration, water temperature, dissolved oxygen, pH) and hydrometeorological variables (stream discharge, solar radiation) under hydrologically stable conditions. The study was carried out in 2006, within the 42 km2 forested Padež stream watershed in the southwestern part of Slovenia, which is characterized by distinctive hydrogeological settings (flysch) and climate conditions (transitional area between the Mediterranean and continental climate). Fine temporal data resolution (15-min interval) enabled identification of the factors responsible for seasonal variability in the diurnal pattern of the streamwater NO3-N concentrations versus seasonal and diurnal behavior of meteorological and other water chemistry constituents. The observed seasonal variability of in-stream NO3-N daily oscillations indicates the important role of primary production uptake, particularly during seasons when deciduous vegetation is dormant and light levels in the stream are high. Highest daily NO3-N concentration amplitudes (0.3 mg/l-N) and daily changes in the NO3-N flux (0.4–0.5 g/s-N) were observed in spring; the NO3-N concentration oscillations in summer showed a considerably smaller effect of the in-stream uptake (maximum NO3-N daily concentration amplitude 0.1 mg/l-N; daily change in the NO3-N flux 0.02 g/s-N). Seasonal shifts in the timing of daily maximum (up to 6 h) and minimum NO3-N concentrations (between 1 and 3 h) provided some additional indications of seasonal changes in the in-stream primary production uptake and its relation to the terrestrial component of the forested watershed.

Human activities have greatly increased the input of biologically available nitrogen (N) from land-based sources to aquatic ecosystems; yet few studies have examined how human actions influence N export in regions with a strong seasonality in water availability. In this study, we quantified N inputs and outputs for 23 California watersheds and examined how climate, hydrology, and land use practices influenced watershed N export. N inputs ranged from 581 to 11,234 kg N km−2 year−1 among watersheds, with 80% of total input for the region originating from agriculture (inorganic fertilizer, manure, and legumes). Of the potential N sources examined, mean annual concentrations of dissolved organic N and dissolved inorganic N in study rivers correlated most strongly with manure N input (r 2 = 0.54 and 0.53, respectively). Seasonal N export varied by basin and was correlated with climate, anthropogenic N inputs, and reservoir releases. Fractional export of watershed N inputs by study rivers annually was small (median of 8%) and scaled exponentially with runoff (r = 0.66). Collectively, our results show that anthropogenic activities have altered both the magnitude and timing of watershed N export in California and suggest that targeted management in specific locations and times of the year could reduce N export to downstream systems in the region.

This study evaluated the sources, sinks, and factors controlling net export of nitrogen (N) from watersheds on the west coast of the US. We calculated input of new N to 22 watersheds for 1992 and 2002. 1992 inputs ranged from 541 to 11,644 kg N km−2 year−1, with an overall area-weighted average of 1,870 kg N km−2 year−1. In 2002, the range of inputs was 490–10,875 kg N km−2 year−1, averaging 2,158 kg N km−2 year−1. Fertilizer was the most important source of new N, averaging 956 (1992) and 1,073 kg N km−2 year−1 (2002). Atmospheric deposition was the next most important input, averaging 833 (1992) and 717 kg N km−2 year−1 (2002), followed by biological N fixation in agricultural lands. Riverine N export, calculated based on measurements taken at the furthest downstream USGS water quality monitoring station, averaged 165 (1992) and 196 kg N km−2 year−1 (2002), although data were available for only 7 watersheds at the latter time point. Downstream riverine N export was correlated with variations in streamflow (export = 0.94 × streamflow − 5.65, R 2 = 0.66), with N inputs explaining an additional 16% of the variance (export = 1.06 × streamflow + 0.06 × input − 227.78, R 2 = 0.82). The percentage of N input that is exported averaged 12%. Percent export was also related to streamflow (%export = 0.05 × streamflow − 2.61, R 2 = 0.60). The correlations with streamflow are likely a result of its large dynamic range in these systems. However, the processes that control watershed N export are not yet completely understood.

Human activities have greatly increased the transport of biologically available nitrogen (N) through watersheds to potentially sensitive coastal ecosystems. Lentic water bodies (lakes and reservoirs) have the potential to act as important sinks for this reactive N as it is transported across the landscape because they offer ideal conditions for N burial in sediments or permanent loss via denitrification. However, the patterns and controls on lentic N removal have not been explored in great detail at large regional to global scales. In this paper we describe, evaluate, and apply a new, spatially explicit, annual-scale, global model of lentic N removal called NiRReLa (Nitrogen Retention in Reservoirs and Lakes). The NiRReLa model incorporates small lakes and reservoirs than have been included in previous global analyses, and also allows for separate treatment and analysis of reservoirs and natural lakes. Model runs for the mid-1990s indicate that lentic systems are indeed important sinks for N and are conservatively estimated to remove 19.7 Tg N year−1 from watersheds globally. Small lakes (

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.

Dissolved organic carbon (DOC) dynamics in streams is important, yet few studies focus on DOC dynamics in Midwestern streams during storms. In this study, stream DOC dynamics during storms in two Midwestern watersheds with contrasting land uses, the change in character of stream DOC during storms, and the usability of DOC as a hydrologic tracer in artificially drained landscapes of the Midwest are investigated. Major cation/DOC concentrations, and DOC specific UV absorbance (SUVA) and fluorescence index (FI) were monitored at 2–4 h intervals during three spring storms. Although DOC is less aromatic in the mixed land use watershed than in the agricultural watershed, land use has little impact on stream DOC concentration during storms. For both watersheds, DOC concentration follows discharge, and SUVA and FI values indicate an increase in stream DOC aromaticity and lignin content during storms. The comparison of DOC/major cation flushing dynamics indicates that DOC is mainly exported via overland flow/macropore flow. In both watersheds, the increase in DOC concentration in the streams during storms corresponds to a shift in the source of DOC from DOC originating from mineral soil layers of the soil profile at baseflow, to DOC originating from surficial soil layers richer in aromatic substances and lignin during storms. Results also suggest that DOC, SUVA and FI could be used as hydrologic tracers in artificially drained landscapes of the Midwest. These results underscore the importance of sampling streams for DOC during high flow periods in order to understand the fate of DOC in streams.

We studied the spatial and temporal variation in O2 and dissolved inorganic carbon (DIC) forms concentrations in ten subtropical watersheds located in the state of Sao Paulo, Brazil, with different degrees of impact by urbanization and land-use changes. Additionally, we used stable carbon isotopic composition of DIC to explain observed patterns. We found that land-cover changes and watershed geology are the main drivers of DIC distribution. Land-cover/use changes influence the riverine DIC in two ways: by replacing the original Cerrado 3 (C3)-type forest vegetation by C4-type vegetation composed of grasses (pasture), and by sugarcane. Most domestic sewage is dumped untreated into rivers in the state of Sao Paulo. Consequently, in the most densely populated watersheds, sewage is an important source of labile carbon and consequently of DIC to rivers. In terms of geology, although silicate weathering that produces kaolinite is the main type of weathering in the watersheds, the weathering of carbonate cements present in the geological formations of the western portion of the state of Sao Paulo are also an important source of DIC to rivers.

The watershed of the Altamaha River, Georgia, is one of the largest in the southeastern U.S., draining 36,718 km2 (including parts of metro Atlanta). We calculated both nitrogen (fertilizer, net food and feed import, atmospheric deposition, and biological N fixation in agricultural and forest lands) and phosphorus (fertilizer and net food and feed import) inputs to the watershed for 6 time points between 1954 and 2002. Total nitrogen inputs rose from 1,952 kg N km−2 yr−1 in 1954 to a peak of 3,593 kg N km−2 yr−1 in 1982 and then declined to 2,582 kg N km−2 yr−1 by 2002. Phosphorus inputs rose from 409 kg P km−2 yr−1 in 1954 to 532 kg P km−2 yr−1 in 1974 before declining to 412 kg P km−2 yr−1 in 2002. Fertilizer tended to be the most important input of both N and P to the watershed, although net food and feed import increased in importance over time and was the dominant source of N input by 2002. When considered on an individual basis, fertilizer input tended to be highest in the middle portions of the watershed (Little and Lower Ocmulgee and Lower Oconee sub-watersheds) whereas net food and feed imports were highest in the upper reaches (Upper Oconee and Upper Ocmulgee sub-watersheds). Although the overall trend in recent years has been towards decreases in both N and P inputs, these trends may be offset due to continuing increases in animal and human populations.

Increased export of biologically available nitrogen (N) to the coastal zone is strongly linked to eutrophication, which is a major problem in coastal marine ecosystems (NRC (2000) Clean Coastal Waters: Understanding and Reducing the Effects of Nutrient Pollution. National Academy Press, Washington, DC; Bricker et al. (1999) National Estuarine Eutrophication Assessment. Effects of nutrient enrichment in the nation’s estuaries. NOAA-NOS Special Projects Office, Silver Spring, MD). However, not all of the nitrogen input to a watershed is exported to the coast (Howarth et al. (1996) Biogeochemistry 35:75–139; Jordan and Weller (1996) Bioscience 46:655–664). Global estimates of nitrogen export to coasts have been taken to be 25% of watershed input, based largely on northeastern U.S. observations (Galloway et al. (2004) Biogeochemistry 70:153–226; Boyer et al. (2006) Global Biogeochem Cycle 20:Art. No. GB1S91). We applied the N budgeting methodology developed for the International SCOPE Nitrogen project (Howarth et al. (1996) Biogeochemistry 35:75–139; Boyer et al. (2002) Biogeochemistry 57:137–169) to 12 watersheds in the southeastern U.S., and compared them with estimates of N export for 16 watersheds in the northeastern U.S. (Boyer et al. (2002) Biogeochemistry 57:137–169). In southeastern watersheds, average N export was only 9% of input, suggesting the need for downward revision of global estimates. The difference between northern and southern watersheds is not a function of the absolute value of N inputs, which spanned a comparable range and were positively related to export in both cases. Rather, the proportion of N exported was significantly related to average watershed temperature (% N export = 58.41 e−0.11 * temperature; R 2 = 0.76), with lower proportionate nitrogen export in warmer watersheds. In addition, we identified a threshold in proportionate N export at 38°N latitude that corresponds to a reported breakpoint in the rate of denitrification at 10–12°C. We hypothesize that temperature, by regulating denitrification, results in increased proportionate N export at higher latitudes. Regardless of the mechanism, these observations suggest that temperature increases associated with future climate change may well reduce the amount of nitrogen that reaches estuaries, which will have implications for coastal eutrophication.

Several studies relating land cover to stream properties have used sample sizes of more than 100 watersheds, but the variance that they explain is moderate to low (R 2 less than 50%), limiting the predictive value of these studies when their models are applied to watersheds that were not included in the models’ development. We hypothesize that this is due to the increases in variation that occur with increases in sample size and in the geographic scales of the areas in which the watersheds are distributed. Land cover alone cannot explain all of that variation; more predictors must be considered. Conversely, models with high explicative power would require relatively small sample sizes distributed over small areas. This hypothesis was evaluated sampling 17 watersheds from southern Chile’s Lake Region, for which we developed regressive models between land cover/watershed area/precipitation/geomorphology and stream properties (i.e., conductivity, temperature). With a maximum n = 15 watersheds, on a regional scale, a poorly explained variation in hydrologic variables (mean 37–49%) was obtained. The R 2 increased slightly, to 45–52%, when precipitation was included as a predictor. In half of the cases analyzed, the models improved when geomorphology was considered as an additional predictor (60–66%), supporting our hypothesis. Furthermore, when our analysis was restricted to a narrower latitudinal span (n = 9), the R 2 was much stronger (68–87%) when only land cover and watershed area were included as predictors. These percentages also increased when more predictors were incorporated. Nevertheless, a portion of unexplained variance remained that would require the consideration of more predictors, such as geology and edaphology. The documented trade-off provides evidence that argues against the spatial generality of land cover/stream property models.

To evaluate the effect of human activities on the amount of nitrogen (N) transported to the Three Gorges Dam (TGD), we have developed and applied a model to estimate the riverine N transport from watersheds draining into the upper Changjiang River basin. By using this model and a database of agricultural statistics, we study the temporal and spatial changes in N inputs to watersheds and surface waters. The total amount of N transported to the surface drainage waters from the agro-ecosystem in 2000 showed a 2.9-fold increase over that in 1980. Considering a constant (37%) loss rate from the river, the annual amount of N transported to the TGD from the agro-ecosystem of the Changjiang river upper basin was about 0.35 × 106, 0.47 × 106, 0.59 × 106, 0.64 × 106 and 1.01 × 106 t in 1980, 1985, 1990, 1995, and 2000, respectively. Further, the transported amount of new anthropogenic reactive N approximately quadrupled in 2000, while the amount of riverine N due to rural human waste varied slightly. Of the total N transported to surface drainage waters in 10 watersheds in 2000, the Jialingjiang watershed accounted for 35%; the TGD region, 15%; and the Toujiang, Wujiang and Minjiang watersheds, 11% each. In 1980, the N sources were concentrated in the rural areas surrounding Chendu City and Chongqing City; however, these sources considerably expanded in the 1990s. The increased use of synthetic fertilizers and the decrease in the fertilizer N-use efficiency are implicated as major causal factors of increased riverine N transport; the calculated amount of N transported to the main tributaries agrees well with previously reported data.

Anthropogenic actions are altering fluxes of nitrogen (N) in the biosphere at unprecedented rates. Efforts to study these impacts have concentrated in the Northern hemisphere, where experimental data are available. In tropical developing countries, however, experimental studies are lacking. This paper summarizes available data and assesses the impacts of human activities on N fluxes in Puerto Rico, a densely populated Caribbean island that has experienced drastic landscape transformations over the last century associated with rapid socioeconomic changes. N yield calculations conducted in several watersheds of different anthropogenic influences revealed that disturbed watersheds export more N per unit area than undisturbed forested watersheds. Export of N from urban watersheds ranged from 4.8 kg ha−1 year−1 in the Ri o Bayamon watershed to 32.9 kg ha−1 year−1 in the highly urbanized Rio Piedras watershed and 33.3 kg ha−1 year−1 in the rural-agricultural Rio Grande de Anasco watershed. Along with land use, mean annual runoff explained most of the variance in fluvial N yield. Wastewater generated in the San Juan Metropolitan Area receives primary treatment before it is discharged into the Atlantic Ocean. These discharges are N-rich and export large amounts of N to the ocean at a rate of about 140 kg ha−1 year−1. Data on wet deposition of inorganic N (NH 4 + + NO 3 − ) suggest that rates of atmospheric N deposition are increasing in the pristine forests of Puerto Rico. Stationary and mobile sources of NOx (NO+NO2) and N2O generated in the large urban centers may be responsible for this trend. Comprehensive measurements are required in Puerto Rico to quantitatively characterize the local N cycle. More research is required to assess rates of atmospheric N deposition, N fixation in natural and human-dominated landscapes, N-balance associated with food and feed trade, and denitrification.

The importance of snowmelt and spring rainfall to water and nutrient exports from macro-scale watersheds (>1000 km2) is not well established. Data collected from the Androscoggin River watershed (Maine and New Hampshire) between February 1999 and March 2002 show that the 90-day spring melt period accounted for 39–57% of total annual discharge and is likely driven both by snowpack melting and spring rainfall. While large loads of dissolved inorganic nitrogen (DIN) are delivered to the watershed from snowmelt and rain (from 1.16× 106 to 1.61× 106 kg N over the study years), only one third of this N load is exported from the basin during the snowmelt period (0.40× 106–0.48 × 106 kg N). Despite reduced residence time and temperature limitations on biological N retention, there is a poor mass balance between DIN input to the watershed and the nitrogen exported from mouth of the river. Inferences from a geochemical hydrograph separation suggests that approximately 51–63% of the water leaving the mouth of the Androscoggin river is from these ‘new’ water sources (rain and snowmelt) while 37–49% is from DIN depleted soil and groundwater. Mixing of water from different sources, as well as nutrient retention by dams in the upper watershed, may account for the large discrepancy between DIN inputs and exports from this watershed.

We tested the hypothesis that reservoirs with low water residence time and autochthonous production influence river biogeochemistry in eutrophied river systems draining cultivated watersheds. The effect of a single artificial water reservoir and consecutive reservoirs on silica (Si) river fluxes is exemplified by the moderately dammed Vistula River and the heavily regulated Daugava River that are compared with the practically undammed Oder River. The sum of the discharge weighted annual mean biogenic silica (BSi) and dissolved silicate (DSi) concentrations in the rivers Oder, Vistula and Daugava were about 160 μ M (40 + 120 μ M), 150 μ M (20 + 130 μ M) and 88 μ M (6 + 82 μ M), respectively. Assuming BSi and DSi concentrations as observed in the Oder River as typical for eutrophied but undammed rivers, complete trapping of this BSi could have lowered Si fluxes to the Baltic Sea from rivers with cultivated watersheds by 25%. The superimposed effect of hydrological alterations on reduced Si land–sea fluxes is demonstrated by studies in the boreal/subarctic and oligotrophic rivers Kalixalven and Luealven. The DSi yield of the heavily dammed Lulealven (793 kg km−2 yr−1) constituted only 63% of that was found in the unregulated Kalixalven (1261 kg km−2 yr−1), despite the specific runoff of the Lulealven (672 mm m−2 yr−1) being 19% higher than that of theKalixalven (563 mm m−2 yr−1); runoff normalized DSi yield of the former, regulated watershed, was only half the DSi yield of the latter, unperturbed watershed. Based on these findings, it is hypothesized here that perturbed surface water–groundwater interactions are the major reasons for the reduced annual fluctuations in DSi concentrations as also seen in the heavily dammed and eutrophic river systems such as the Daugava and Danube.

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

Some of the largest riverine N fluxes in the continental USA have been observed in agricultural regions with extensive artificial subsurface drainage, commonly called tile drainage. The degree to which high riverine N fluxes in these settings are due to high net N inputs (NNI), greater transport efficiency caused by the drainage systems, or other factors is not known. The objective of this study was to evaluate the role of tile drainage by comparing NNI and riverine N fluxes in regions of Illinois with similar climate and crop production practices but with different intensities of tile drainage. Annual values of NNI between 1940 and 1999 were estimated from county level agricultural production statistics and census estimates of human population. During 1945–1961, riverine nitrate flux in the extensively tile drained region averaged 6.6 kg N ha−1 year−1 compared to 1.3 to 3.1 kg N ha−1 for the non-tile drained region, even though NNI was greater in the non-tile drained region. During 1977–1997, NNI to the tile-drained region had increased to 27 kg N ha−1 year−1 and riverine N flux was approximately 100% of this value. In the non-tile-drained region, NNI was approximately 23 kg N ha−1 year−1 and riverine N flux was between 25% and 37% of this value (5 to 9 kg N ha−1 year−1). Denitrification is not included in NNI and, therefore, any denitrification losses from tile-drained watersheds must be balanced by other N sources, such as depletion of soil organic N or underestimation of biological N fixation. If denitrification and depletion of soil organic N are significant in these basins, marginal reductions in NNI may have little influence on riverine N flux. If tile drained cropland in Illinois is representative of the estimated 11 million ha of tile drained cropland throughout the Mississippi River Basin, this 16% of the drainage area contributed approximately 30% of the increased nitrate N flux in the Lower Mississippi River that occurred between 1955 and the 1990s.

The importance of lotic systems as sinks for nitrogen inputs is well recognized. A fraction of nitrogen in streamflow is removed to the atmosphere via denitrification with the remainder exported in streamflow as nitrogen loads. At the watershed scale, there is a keen interest in understanding the factors that control the fate of nitrogen throughout the stream channel network, with particular attention to the processes that deliver large nitrogen loads to sensitive coastal ecosystems. We use a dynamic stream transport model to assess biogeochemical (nitrate loadings, concentration, temperature) and hydrological (discharge, depth, velocity) effects on reach-scale denitrification and nitrate removal in the river networks of two watersheds having widely differing levels of nitrate enrichment but nearly identical discharges. Stream denitrification is estimated by regression as a nonlinear function of nitrate concentration, streamflow, and temperature, using more than 300 published measurements from a variety of US streams. These relations are used in the stream transport model to characterize nitrate dynamics related to denitrification at a monthly time scale in the stream reaches of the two watersheds. Results indicate that the nitrate removal efficiency of streams, as measured by the percentage of the stream nitrate flux removed via denitrification per unit length of channel, is appreciably reduced during months with high discharge and nitrate flux and increases during months of low-discharge and flux. Biogeochemical factors, including land use, nitrate inputs, and stream concentrations, are a major control on reach-scale denitrification, evidenced by the disproportionately lower nitrate removal efficiency in streams of the highly nitrate-enriched watershed as compared with that in similarly sized streams in the less nitrate-enriched watershed. Sensitivity analyses reveal that these important biogeochemical factors and physical hydrological factors contribute nearly equally to seasonal and stream-size related variations in the percentage of the stream nitrate flux removed in each watershed.