Landscape-level nitrogen import and export in an ecosystem with complex terrain, Colorado Front Range

Knowledge of import, export, and transport of nitrogen (N) in headwater catchments is essential for understanding ecosystem function and water quality in mountain ecosystems, especially as these ecosystems experience increased anthropogenic N deposition. In this study, we link spatially explicit soil and stream data at the landscape scale to investigate import, export and transport of N in a 0.89?km² site at the alpine-subalpine ecotone in the Front Range of the Rocky Mountains, Colorado, U.S.A. For two of the major N inputs to our site, N deposition in the snowpack and N fixation, a complementary relationship was found across the study site, with greater abundance of N-fixing plants in areas with less snow and substantial snow inputs in areas with low N fixer abundance. During the initial phases of snowmelt, mixing model end members for oxygen isotopes in nitrate (NO₃ ^?) indicated that a substantial quantity of NO₃ ^? is transported downhill into the forested subalpine without being assimilated by soil microbes. After this initial pulse, much less NO₃ ^? entered the stream and most but not all of it was microbial in origin. Rising δ¹⁵N in stream NO₃ ^? indicated greater influence of fractionating processes such as denitrification later in the season. NO₃ ^? from both atmospheric and microbial sources was not exported from our site because it was consumed within the first several hundred meters of the stream; ultimately, N exports were in the form of dissolved organic nitrogen (DON) and particulate N (PN). The results of this study suggest that the highest elevation dry alpine meadows rely more heavily on N fixation as an N source and experience less of the effects of anthropogenic N deposition than mid and lower elevation areas that have more snow. Our data also suggest that mid-elevation krummholz, moist meadows, and talus slopes are exporting N as NO₃ ^? shortly after the onset of snowmelt, but that this NO₃ ^? is rapidly consumed as the stream flows through the subalpine forest. This consumption by assimilation and/or denitrification currently provides a buffer against increased inorganic N availability downstream.     

河流流量对流域下垫面特性的响应

以美国切斯比克湾地区为例,对该区域150个小流域的下垫面特性(包括土地利用类型、地面不透水系数和土壤物理属性)进行了提取,根据1984—2004年间逐日流量观测数据计算出了33个水文指标,运用逐步回归方法在不同地理区分析了9种下垫面特性对其中17个重要水文指标的影响。结果表明:随着草地和林地比例的增加,流量趋于减小、流量变化趋于稳定,随着建设用地和不透水层的增加,流量增加、流量变化剧烈,随着土壤水文组等级的升高,流量减少;在整个切斯比克湾流域,对流域下垫面特性响应最为显著的水文指标是高脉冲个数及历时,在阿巴拉契亚高地地区响应最为显著的水文指标是年极值流量、高脉冲个数及历时,在皮德蒙特山地响应最为显著的水文指标是高脉冲个数及历时,在沿海平原地区响应最为显著的水文指标是高脉冲个数及历时、流量变化的速率与频率。     

Changes in the character of DOC in streams during storms in two Midwestern watersheds with contrasting land uses

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.     

Nitrogen and phosphorus budgets for a tropical watershed impacted by agricultural land use: Guayas, Ecuador

Large-scale changes in land use are occurring in many tropical regions, with significant impacts on nitrogen and phosphorus biogeochemistry. In this study we examine the relationships between land use, anthropogenic nutrient inputs, and riverine nutrient exports in a major agricultural watershed of the Pacific coast of South America, the Guayas River basin of Ecuador. We present comprehensive nutrient budgets for nitrogen (N) and phosphorous (P) for the Guayas River basin and 10 sub-watersheds. We quantify the four major anthropogenic nutrient fluxes into and out of the region: N and P fertilizer application, N fixation by leguminous crops, net import/export of N and P in agricultural products (food and feed), and atmospheric deposition. We also estimate inputs of N from biological N fixation in forests and of P from weathering sources in soils and bedrock. The sum of these sources represents net inputs of N and P to each watershed region. Overall, synthetic fertilizers are the largest input to the Guayas Basin for N (53%) and P (57%), and the largest outputs are N and P in crops. Losses of N and P in river export account for 14–38% of total N and P inputs, and there is significant accumulation of N and P, or unmeasured forms of N and P export, in most of the sub-basins. Nutrient balances are indicative of the sustainability of land use practices in a region, where a negative balance of N or P indicates nutrient depletion and subsequent loss of soil fertility, yield, and economic viability. Although the nutrient balance of the entire Guayas Basin is positive, there are negative or near zero balances in two sub-watersheds with extensive banana, coffee and permanent crops. In these basins, degradation of soil quality may be occurring due to these net nutrient losses. Our data show that nutrients are leaving the basin primarily as export crops, with riverine losses of nutrients smaller than crop exports. Nonetheless, there is a direct relationship between nutrient inputs and river outputs, suggesting that agricultural management practices in the basin may have direct impacts on N and P delivery to the highly productive Guayas estuary.     

Minimal response in watershed nitrate export to severe soil frost raises questions about nutrient dynamics in the Hubbard Brook experimental forest

Experimental and theoretical work emphasize the role of plant nutrient uptake in regulating ecosystem nutrient losses and predict that forest succession, ecosystem disturbance, and continued inputs of atmospheric nitrogen (N) will increase watershed N export. In ecosystems where snowpack insulates soils, soil-frost disturbances resulting from low or absent snowpack are thought to increase watershed N export and may become more common under climate-change scenarios. This study monitored watershed N export from the Hubbard Brook Experimental Forest (HBEF) in response to a widespread, severe soil-frost event in the winter of 2006. We predicted that nitrate (NO₃ ⁻) export following the disturbance would be high compared to low background streamwater NO₃ ⁻ export in recent years. However, post-disturbance annual NO₃ ⁻ export was the lowest on record from both reference (undisturbed) and treated experimental harvest or CaSiO₃ addition watersheds. These results are consistent with other studies finding greater than expected forest NO₃ ⁻ retention throughout the northeastern US and suggest that changes over the last five decades have reduced impacts of frost events on watershed NO₃ ⁻ export. While it is difficult to parse out causes from a complicated array of potential factors, based on long-term records and watershed-scale experiments conducted at the HBEF, we propose that reduced N losses in response to frost are due to a combination of factors including the long-term legacies of land use, process-level alterations in N pathways, climate-driven hydrologic changes, and depletion of base cations and/or reduced soil pH due to cumulative effects of acid deposition.     

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.     

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.     

The influence of watershed characteristics on nitrogen export to and marine fate in Hood Canal,Washington, USA

Hood Canal, Washington, USA, is a poorly ventilated fjord-like sub-basin of Puget Sound that commonly experiences hypoxia. This study examined the influence of watershed soils, vegetation, physical features, and population density on nitrogen (N) export to Hood Canal from 43 tributaries. We also linked our watershed study to the estuary using a salinity mass balance model that calculated the relative magnitude of N loading to Hood Canal from watershed, direct precipitation, and marine sources. The overall flow-weighted total dissolved N (TDN) and particulate N input concentrations to Hood Canal were 152 and 49 μg l⁻¹, respectively. Nitrate and dissolved organic N comprised 64 and 29% of TDN, respectively. The optimal regression models for TDN concentration and areal yield included a land cover term suggesting an effect of N-fixing red alder (Alnus rubra) and a human population density term (suggesting onsite septic system (OSS) discharges). There was pronounced seasonality in stream water TDN concentrations, particularly for catchments with a high prevalence of red alder, with the lowest concentrations occurring in the summer and the highest occurring in November–December. Due to strong seasonality in TDN concentrations and in particular stream flow, over 60% of the TDN export from this watershed occurred during the 3 month period of November–January. Entrainment of marine water into the surface layer of Hood Canal accounted for ≈98% of N loading to the euphotic zone of this estuary, and in a worst case scenario OSS N inputs contribute ≈0.5% of total N loading. Domestic wastewater discharges and red alders appear to be a very important N source for many streams, but a minor nutrient source for the estuary as a whole.     

A geospatial approach for assessing denitrification sinks within lower-order catchments

Local decision makers can influence land use practices that alter N loading and processing within the drainage basin of lower-order stream reaches. Because many practices reduce water retention times and alter the timing and pathways of water flow, local decisions regarding land use can potentially exert a major influence on watershed N export. We illustrate a geospatial approach for assessing the role of denitrification sinks in watershed N delivery at the local level using: (a) widely available geospatial data, (b) current findings from peer-reviewed literature, (c) USGS stream gage data, and (d) locally based data on selected stream attributes. With high resolution, high quality GIS data increasingly available to local communities, they are now in a position to guide local management of watershed N by targeting upland source controls and by identifying landscape sinks for protection and/or restoration. We characterize riparian wetlands, lentic water bodies, and stream reaches as N sinks in the landscape and use geospatial particle tracking to estimate flow paths from N sources and evaluate N removal within sinks. We present an example analysis of the Chickasheen drainage basin, RI, USA, comparing N flux from three equivalent hypothetical N source areas situated in different regions of the watershed and illustrating the role of each N sink type in mediating N flux. Because our goal is to generate a tool that is used by and useful to decision makers we are exploring methods to better understand how decision makers understand and respond to the manner in which information is presented.     

Anthropogenic disturbance and streams: land use and land‐use change affect stream ecosystems via multiple pathways

1. Ecosystems are strongly influenced by land use practices. However, identifying the mechanisms behind these influences is complicated by the many potential pathways (often indirect) between land use and ecosystems and by the long‐lasting effects of past land use. To support ecosystem restoration and conservation efforts, we need to better understand these indirect and lasting effects. 2. We constructed structural equation models (SEM) to evaluate the direct and indirect effects of contemporary (2002) land use (agriculture and development) and change in land use from 1952 to 2002 on present‐day streams (n = 190) in Maryland, U.S.A. Additional variables examined included site location, system size, altitude, per cent sand in soils, riparian condition, habitat quality, stream water NO₃‐N and benthic macroinvertebrate and fish measures of stream condition. Our first SEM (2002 Land Use) included the proportions of contemporary agriculture and development in catchments in the model. The second SEM (Land Use Change) included five measures of land use change (proportion agricultural in both times, developed in both times, agricultural in 1952 and developed in 2002, forested in 1952 and developed in 2002 and agricultural in 1952 and forested in 2002). 3. The data set fit both SEMs well. The 2002 Land Use model explained 71% of variation in NO₃‐N and 55%, 42% and 38% of variation in riffle quality, macroinvertebrate condition and fish condition, respectively. The Land Use Change model explained similar amounts of variation in NO₃‐N (R² = 0.72), riffle quality (R² = 0.57) and macroinvertebrate condition (R² = 0.44) but slightly more variation in fish condition (R² = 0.43). 4. Both models identified pathways through which landscape variables affect stream responses, including negative direct effects of latitude on macroinvertebrate and fish conditions and positive direct and indirect effects of altitude on NO₃‐N, riffle quality and macroinvertebrate and fish conditions. The 2002 Land Use model showed contemporary development and agriculture had positive total effects on NO₃‐N (both through direct pathways); contemporary development had negative effects on macroinvertebrate condition. The Land Use Change model showed that contemporary developed land that was forested in 1952 had no effects on NO₃‐N; current developed land that was developed or agricultural in 1952 showed positive effects on NO₃‐N. Forests that were agricultural in 1952 had negative effects on NO₃‐N, suggesting reduced NO₃‐N export with reforestation. The Land Use Change model also showed negative total effects of all types of contemporary developed land (developed, agricultural or forested in 1952) on benthic condition. Developed land that was forested in 1952 had negative effects on fish condition. Forest sites that were agricultural in 1952 had negative effects on fish and macroinvertebrate conditions, suggesting a long‐term imprint of abandoned agriculture in stream communities. 5. Our analyses (i) identified multiple indirect effects of contemporary land use on streams, (ii) showed that current land uses with different land use histories can exhibit different effects on streams and (iii) demonstrated an imprint of land use lasting >50 years. Knowledge of these indirect and long‐term effects of land use will help to conserve and restore streams.     

Biogeochemistry of unpolluted forested watersheds in the Oregon Cascades: temporal patterns of precipitation and stream nitrogen fluxes

We analyzed long-term organic and inorganic nitrogen inputs and outputs in precipitation and streamwater in six watersheds at the H.J. Andrews Experimental Forest in the central Cascade Mountains of Oregon. Total bulk N deposition, averaging 1.6 to 2.0 kg N ha^–1 yr^–1, is low compared to other sites in the United States and little influenced by anthropogenic N sources. Streamwater N export is also low, averaging <1 kg ha^–1 yr^–1. DON is the predominant form of N exported from all watersheds, followed by PON, NH₄-N, and NO₃-N. Total annual stream discharge was a positive predictor of annual DON output in all six watersheds, suggesting that DON export is related to regional precipitation. In contrast, annual discharge was a positive predictor of annual NO₃-N output in one watershed, annual NH₄-N output in three watersheds, and annual PON output in three watersheds. Of the four forms of N, only DON had consistent seasonal concentration patterns in all watersheds. Peak streamwater DON concentrations occurred in November-December after the onset of fall rains but before the peak in the hydrograph, probably due to flushing of products of decomposition that had built up during the dry summer. Multiple biotic controls on the more labile nitrate and ammonium concentrations in streams may obscure temporal DIN flux patterns from the terrestrial environment. Results from this study underscore the value of using several watersheds from a single climatic zone to make inferences about controls on stream N chemistry; analysis of a single watershed may preclude identification of geographically extensive mechanisms controlling N dynamics.     

Decadal-scale Dynamics of Water, Carbon and Nitrogen in a California Chaparral Ecosystem: DAYCENT Modeling Results

The Mediterranean climate, with its characteristic of dry summers and wet winters, influences the hydrologic and microbial processes that control carbon (C) and nitrogen (N) biogeochemical processes in chaparral ecosystems. These biogeochemical processes in turn determine N cycling under chronic N deposition. In order to examine connections between climate and N dynamics, we quantified decadal-scale water, C and N states and fluxes at annual, monthly and daily time steps for a California chaparral ecosystem in the Sierra Nevada using the DAYCENT model. The daily output simulations of net mineralization, stream flow and stream nitrate (NO₃⁻) export were developed for DAYCENT in order to simulate the N dynamics most appropriate for the abrupt rewetting events characteristic of Mediterranean chaparral ecosystems. Overall, the magnitude of annual modeled net N mineralization, soil and plant biomass C and N, nitrate export and gaseous N emission agreed with those of observations. Gaseous N emission was a major N loss pathway in chaparral ecosystems, in which nitric oxide (NO) is the dominant species. The modeled C and N fluxes of net primary production (NPP), N uptake and N mineralization, NO₃⁻ export and gaseous N emission showed both high inter-annual and intra-annual variability. Our simulations also showed dramatic fire effects on NPP, N uptake, N mineralization and gaseous N emission for three years of postfire. The decease in simulated soil organic C and N storages was not dramatic, but lasted a longer time. For the seasonal pattern, the predicted C and N fluxes were greatest during December to March, and lowest in the summer. The model predictions suggested that an increase in the N deposition rate would increase N losses through gaseous N emission and stream N export in the chaparral ecosystems of the Sierra Nevada due to changes in N saturation status. The model predictions could not capture stream NO₃⁻ export during most rewetting events suggesting that a dry-rewetting mechanism representing the increase in N mineralization following soil wetting needs to be incorporated into biogeochemical models of semi-arid ecosystems.     

Land-Use Change and Stream Water Fluxes: Decadal Dynamics in Watershed Nitrate Exports

Stream water exports of nutrients and pollutants to water bodies integrate internal and external watershed processes that vary in both space and time. In this paper, we explore nitrate (NO₃) fluxes for the 326 km² mixed-land use Fall Creek watershed in central New York for 1972–2005, and consider internal factors such as changes in land use/land cover, dynamics in agricultural production and fertilizer use, and external factors such as atmospheric deposition. Segmented regression analysis was applied independently to dormant and growing seasons for three portions of the period of record, which indicated that stream water NO₃ concentrations increased in both dormant and growing seasons from the 1970s to the early 1990s at all volumes of streamflow discharge. Dormant season NO₃ concentrations then decreased at all flow conditions between the periods 1987–1993 and 1994–2005. Results from a regression-based stream water loading model (LOADEST) normalized to mean annual concentrations showed annual modeled NO₃ concentration in stream water increased by 34% during the 1970s and 1980s (from 1.15 to 1.54 mg l⁻¹), peaked in about 1989, and then decreased by 29% through 2005 (to 1.09 mg l⁻¹). Annual precipitation had the strongest correlation with stream water NO₃ concentrations (r = −0.62, P = 0.01). Among land use factors, corn production for grain was the variable most highly correlated to stream water NO₃ concentrations (r = 0.53, P = 0.01). The strongest associative trend determined using Chi-squared Automatic Interaction Detection (CHAID) was found between stream water NO₃ concentrations and N-equivalence of dairy production (Bonferroni adjusted P value = 0.0003). Large increases in dairy production were coincident with declining nitrate concentrations over the past decade, which suggest that dairy management practices may have improved in the watershed. However, because dairy production in the Fall Creek watershed has been fueled by large increases in feed imports, the environmental costs of feed production have likely been externalized to other watersheds.     

Retention of Nitrogen Following Wildfire in a Chaparral Ecosystem

Wildfires alter nitrogen (N) cycling in Mediterranean-type ecosystems, resetting plant and soil microbial growth, combusting plant biomass to ash, and enhancing N availability in the upper soil layer. This ash and soil N pool (that is, wildfire N) is susceptible to loss from watersheds via runoff and leaching during post-fire rains. Plant and soil microbial recovery may mitigate these losses by sequestering N compounds in new biomass, thereby promoting landscape N retention in N-limited chaparral ecosystems. We investigated the relative balance between wildfire N loss, and plant and soil microbial N uptake and stream N export for an upland chaparral watershed in southern California that burned (61%) in a high-intensity wildfire in 2009 by using a combination of stream, vegetation, soil microbial, and remote sensing analyses. Soil N in the burn scar was 440% higher than unburned soil N in the beginning of the first post-fire wet season and returned within 66 days to pre-fire levels. Stream N export was 1480% higher than pre-fire export during the first post-fire rain and returned within 106 days over the course of the following three rainstorms to pre-fire levels. A watershed-scale N mass balance revealed that 52% of wildfire N could be accounted for in plant and soil microbial growth, whereas 1% could be accounted for in stream export of dissolved nitrogen.     

Regional nitrogen budgets for China and its major watersheds

Since the Changjiang River, Huanghe River and Zhujiang River are the three major rivers in China that are flowing into the Pacific Ocean, this paper addresses nitrogen budgeting, source (input) and sink (output and storage), in these three river valleys, and the China watershed as well. In the China watershed, the anthropogenic reactive N has far exceeded the terrestrial bio-fixed N in nature, and human activities have significantly altered the N cycling in this region. In 1995, the total amount of anthropogenic reactive N in China reached 31.2 Tg with 22.2 Tg coming from synthetic fertilizers and 4.18 Tg from NO_x emission from fossil fuel combustion, and the input of recycling N amounted to 30.5 Tg, consisting mainly of human and animal excrement N, reflecting the intensity of the human activity. The sink of N includes N in the harvested crop, denitrification and storage in agricultural soils, transportation into waterbodies and volatilization of NH₃. N output and storage in soil reached up to 48–53 Tg. Of this amount, 14 Tg was in the harvested crops, 12 Tg stored in agricultural soils, 11 Tg transported into waterbodies, 5 – 10 Tg denitrified in the soils and a limited amount exported through food/feed.In this paper – besides the N budget in the China watershed – the N budgets and especially N transports into waterbodies in the Changjiang, Huanghe and Zhujiang river valleys are estimated.     

Contrasting nutrient exports from a forested and an agricultural catchment in south-eastern Australia

Dissolved organic carbon (DOC) and total and inorganic nitrogen and phosphorus concentrations were determined over 3 years in headwater streams draining two adjacent catchments. The catchments are currently under different land use; pasture/grazing vs plantation forestry. The objectives of the work were to quantify C and nutrient export from these landuses and elucidate the factors regulating export. In both catchments, stream water dissolved inorganic nutrient concentrations exhibited strong seasonal variations. Concentrations were highest during runoff events in late summer and autumn and rapidly declined as discharge increased during winter and spring. The annual variation of stream water N and P concentrations indicated that these nutrients accumulated in the catchments during dry summer periods and were flushed to the streams during autumn storm events. By contrast, stream water DOC concentrations did not exhibit seasonal variation. Higher DOC and NO₃ ⁻ concentrations were observed in the stream of the forest catchment, reflecting greater input and subsequent breakdown of leaf-litter in the forest catchment. Annual export of DOC was lower from the forested catchment due to the reduced discharge from this catchment. In contrast however, annual export of nitrate was higher from the forest catchment suggesting that there was an additional NO₃ ⁻ source or reduction of a NO₃ ⁻ sink. We hypothesize that the denitrification capacity of the forested catchment has been significantly reduced as a consequence of increased evapotranspiration and subsequent decrease in streamflow and associated reduction in the near stream saturated area.     

High Atmospheric Nitrate Inputs and Nitrogen Turnover in Semi-arid Urban Catchments

The influx of atmospheric nitrogen to soils and surfaces in arid environments is of growing concern due to increased N emissions and N usage associated with urbanization. Atmospheric nitrogen inputs to the critical zone can occur as wet (rain or snow) or dry (dust or aerosols) deposition, and can lead to eutrophication, soil acidification, and groundwater contamination through leaching of excess nitrate. The objective of this research was to use the δ¹⁵N, δ¹⁸O, and Δ¹⁷O values of atmospheric nitrate (NO₃ ^?) (precipitation and aerosols) and NO₃ ^? in runoff to assess the importance of N deposition and turnover in semi-arid urban watersheds. Data show that the fractions of atmospheric NO₃ ^? exported from all the urban catchments, throughout the study period, were substantially higher than in nearly all other ecosystems studied with mean atmospheric contributions of 38% (min 0% and max 82%). These results suggest that catchment and stream channel imperviousness enhance atmospheric NO₃ ^? export due to inefficient N cycling and retention. In contrast, catchment and stream channel perviousness allow for enhanced N processing and therefore reduced atmospheric NO₃ ^? export. Overall high fractions of atmospheric NO₃ ^? were primarily attributed to slow N turn over in arid/semi-arid ecosystems. A relatively high fraction of nitrification NO₃ ^? (~30%) was found in runoff from a nearly completely impervious watershed (91%). This was attributed to nitrification of atmospheric NH₄ ⁺ in dry-deposited dust, suggesting that N nitrifiers have adapted to urban micro niches. Gross nitrification rates based on NO₃ ^? Δ¹⁷O values ranged from a low 3.04 ± 2 kg NO₃-N km^?2 day^?1 in highly impervious catchments to a high of 10.15 ± 1 kg NO₃-N km^?2 day^?1 in the low density urban catchment. These low gross nitrification rates were attributed to low soil C:N ratios that control gross autotrophic nitrification by regulating gross NH₄ ⁺ production rates.     

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.     

Proton production from nitrogen transformation drives stream export of base cations in acid-sensitive forested watersheds

The biogeochemical cycles of nitrogen (N) and base cations (BCs), (i.e., K⁺, Na⁺, Ca²⁺, and Mg²⁺), play critical roles in plant nutrition and ecosystem function. Empirical correlations between large experimental N fertilizer additions to forest ecosystems and increased BCs loss in stream water are well demonstrated, but the mechanisms driving this coupling remain poorly understood. We hypothesized that protons generated through N transformation (PPR_N)—quantified as the balance of NH₄⁺ (H⁺ source) and NO₃⁻ (H⁺ sink) in precipitation versus the stream output will impact BCs loss in acid-sensitive ecosystems. To test this hypothesis, we monitored precipitation input and stream export of inorganic N and BCs for three years in an acid-sensitive forested watershed in a granite area of subtropical China. We found the precipitation input of inorganic N (17.71 kg N ha⁻¹ year⁻¹ with 54% as NH₄⁺–N) was considerably higher than stream exported inorganic N (5.99 kg N ha⁻¹ year⁻¹ with 83% as NO₃⁻–N), making the watershed a net N sink. The stream export of BCs (151, 1518, 851, and 252 mol ha⁻¹ year⁻¹ for K⁺, Na⁺, Ca²⁺, and Mg²⁺, respectively) was positively correlated (r = 0.80, 0.90, 0.84, and 0.84 for K⁺, Na⁺, Ca²⁺, and Mg²⁺ on a monthly scale, respectively, P < 0.001, n = 36) with PPR_N (389 mol ha⁻¹ year⁻¹) over the three years, suggesting that PPR_N drives loss of BCs in the acid-sensitive ecosystem. A global meta-analysis of 15 watershed studies from non-calcareous ecosystems further supports this hypothesis by showing a similarly strong correlation between ∑BCs output and PPR_N (r = 0.89, P < 0.001, n = 15), in spite of the pronounced differences in environmental settings. Collectively, our results suggest that N transformations rather than anions (NO₃⁻ and/or SO₄²⁻) leaching specifically, are an important mediator of BCs loss in acid-senstive ecosystems. Our study provides the first definitive evidence that the chronic N deposition and subsequent transformation within the watershed drive stream export of BCs through proton production in acid-sensitive ecosystems, irrespective of their current relatively high N retention. Our findings suggest the N-transformation-based proton production can be used as an indicator of watershed outflow quality in the acid-sensitive ecosystems.