Controls on surface water chemistry in two lake‐watersheds in the Adirondack region of New York: differences in nitrogen solute sources and sinks

The southwestern Adirondack region of New York receives among the highest rates of atmospheric nitrogen (N) deposition in the USA. Atmospheric N deposition to sensitive ecosystems, like the Adirondacks, may increase the acidification of soils through losses of exchangeable nutrient cations, and the acidification of surface waters associated with enhanced mobility of nitrate (NO₃^?). However, watershed attributes, including surficial terrestrial characteristics, in‐lake processing, and geological settings, have been found to complicate the relationships between atmospheric N deposition and N drainage losses. We studied two lake‐watersheds in the southwestern Adirondacks, Grass Pond and Constable Pond, which are located in close proximity (～26 km) and receive similarly high N deposition, but have contrasting watershed attributes (e.g. wetland area, geological settings). Since the difference in the influence of N deposition was minimal, we were able to examine both within‐ and between‐watershed influences of land cover, the contribution of glacial till groundwater inputs, and in‐lake processes on surface water chemistry with particular emphasis on N solutes and dissolved organic carbon (DOC). Monthly samples at seven inlets and one outlet of each lake were collected from May to October in 1999 and 2000. The concentrations of NO₃^? were high at the Grass Pond inlets, especially at two inlets, and NO₃^? was the major N solute at the Grass Pond inlets. The concentrations of likely weathering products (i.e. dissolved Si, Ca²⁺, Mg²⁺, Na⁺) as well as acid neutralizing capacity and pH values, were also particularly high at those two Grass Pond inlets, suggesting a large contribution of groundwater inputs. Dissolved organic N (DON) was the major N solute at the Constable Pond inlets. The higher concentrations of DON and DOC at the Constable Pond inlets were attributed to a large wetland area in the watershed. The DOC/DON ratios were also higher at the Constable Pond inlets, possibly due to a larger proportion of coniferous forest area. Although DON and DOC were strongly related, the stronger relationship of the proportion of wetland area with DOC suggests that additional factors regulate DON. The aggregated representation of watershed physical features (i.e. elevation, watershed area, mean topographic index, hypsometric‐analysis index) was not clearly related to the lake N and DOC chemistry. Despite distinctive differences in inlet N chemistry, NO₃^? and DON concentrations at the outlets of the two lakes were similar. The lower DOC/DON ratios at the lake outlets and at the inlets having upstream ponds suggest the importance of N processing and organic N sources within the lakes. Although an inverse relationship between NO₃^? and DOC/DON has been suggested to be indicative of a N deposition gradient, the existence of this relationship for sites that receive similar atmospheric N deposition suggest that the relationship between NO₃^? and the DOC/DON ratio is derived from environmental and physical factors. Our results suggest that, despite similar wet N deposition at the two watershed sites, N solutes entering lakes were strongly affected by hydrology associated with groundwater contribution and the presence of wetlands, whereas N solutes leaving lakes were strongly influenced by in‐lake processing. Copyright © 2006 John Wiley & Sons, Ltd.     

Factors controlling nitrogen and dissolved organic carbon exports across timescales in two watersheds with different land uses

Investigating factors controlling the temporal patterns of nitrogen (N) and dissolved organic carbon (DOC) exports on the basis of a comparative study of different land uses is beneficial for managing water resources, especially in agricultural watersheds. We focused our research on an agricultural watershed (AW) and a forested watershed (FW) located in the Shibetsu watershed of eastern Hokkaido, Japan, to investigate the temporal patterns of N and DOC exports and factors controlling those patterns at different timescales (inter‐annual, seasonal, and hydrological event scales). Results showed that the annual patterns of N and DOC exports significantly varied over time and were probably controlled by climate. Higher discharge volumes in 2003, a wet year, showed higher N and DOC loadings in both watersheds. However, this process was also regulated by land use associated with N inputs. Higher concentrations and loadings were shown in the agricultural watershed. At the seasonal scale, N and DOC exports in the AW and the FW were more likely controlled by sources associated with land use. The Total N (TN) and Nitrate‐N (NO₃^?‐N) had higher concentrations during snowmelt season in the AW, which may be attributed to manure application in late autumn or early winter in the agricultural watershed. Concentrations of TN, NO₃^?‐N, dissolved organic nitrogen (DON), and DOC showed higher values during the summer rainy season in the FW, related to higher litter decomposition during summer and autumn and the fertilizer application in the agricultural area during summer. Higher DOC concentrations and loadings were observed during the rainy season in the AW, which is probably attributed to higher DOC production related to temperature and microbial activity during summer and autumn in grasslands. Correlations between discharge and concentrations differed during different periods or in different watersheds, suggesting that weather discharge can adequately represent the fact that N export depends on N concentrations, discharge level, and other factors. The differing correlations between N/DOC concentrations and the Si concentration indicated that the N/DOC exports might occur along different flow paths during different periods. During baseflow, the high NO₃^?‐N exports were probably derived from deep groundwater and might have percolated from uplands during hydrological events. During hydrological events, NO₃^?‐N exports may occur along near‐surface flow paths and in deep groundwater, whereas DOC exports could be related to near‐surface flow paths. At the event scale, the relationships between discharge and concentrations of N and DOC were regulated by antecedent soil moisture (shallow groundwater condition) in each watershed. These results indicated that factors controlling N and DOC exports varied at different timescales in the Shibetsu area and that better management of manure application during winter in agricultural lands is urgently needed to control water pollution in streams. Copyright © 2013 John Wiley & Sons, Ltd.     

Hydrochemical behaviour of dissolved nitrogen and carbon in a headwater stream of the Canadian Shield: relevance of antecedent soil moisture conditions

This paper examines the impact of contrasting antecedent soil moisture conditions on the hydrochemical response, here the changes in dissolved nitrogen (NO₃^?, NH₄⁺ and dissolved organic nitrogen (DON)) and dissolved organic carbon (DOC) concentrations, of a first‐order stream during hydrological events. The study was performed in the Hermine, a 5 ha forested watershed of the Canadian Shield. It focused on a series of eight precipitation events (spring, summer and fall) sampled every 2 or 3 h and showing contrasted antecedent moisture conditions. The partition of the eight events between two groups (dry or wet) of antecedent moisture conditions was conducted using a principal component analysis (PCA). The partition was controlled (first axis explained 86% of the variability) by the antecedent streamflow, the streamflow to precipitation ratio Q/P and by the antecedent groundwater depth. The mean H⁺, NO₃^?, NH₄⁺, total dissolved nitrogen and DOC concentrations and electrical conductivity values in the stream were significantly higher following dry antecedent conditions than after wetter conditions had prevailed in the Hermine, although the temporal variability was high (17 to 138%). At the event scale, a significantly higher proportion of the changes in DON, NO₃^?, and DOC concentrations in the stream was explained by temporal variations in discharge compared with the seasonal and annual scales. Two of the key hydrochemical features of the dry events were the synchronous changes in DOC and flow and the frequent negative relationships between discharge and NO₃^?. The DON concentrations were much less responsive than DOC to changes in discharge, whereas NH was not in phase with streamflow. During wet events, the synchronicity between streamflow and DON or NO₃^? was higher than during dry events and discharge and NO₃^? were generally positively linked. Based on these observations, the hydrological behaviour of the Hermine is conceptually compatible with a two‐component model of shallow (DON and DOC rich; variable NO₃^?) and deep (DON and DOC poor; variable NO₃^?) subsurface flow. The high NO₃^? and DOC levels measured at the early stages of dry events reflected the contribution from NO₃^?‐rich groundwaters. The contribution of rapid surface flow on water‐repellent soil materials located close to the stream channel is hypothesized to explain the DOC levels. An understanding of the complex interactions between antecedent soil moisture conditions, the presence of soil nutrients available for leaching and the dynamics of soil water flow paths during storms is essential to explain the fluxes of dissolved nitrogen and carbon in streams of forested watersheds. Copyright © 2007 John Wiley & Sons, Ltd.     

Fluvial carbon export and CO2 efflux in representative nested headwater catchments of the eastern La Plata River Basin

This study involved a baseline evaluation of fluvial carbon export and degas rates in three nested rural catchments (1 to 80 km²) in Taboão, a representative experimental catchment of the Upper Uruguay River Basin. Analyses of the carbon content in stream waters and the catchment carbon yield were based on 4‐year monthly in situ data and statistical modeling using the United States Geological Survey load estimator model. We also estimated p CO₂ and degas fluxes using carbonate equilibrium and gas‐exchange formulas. Our results indicated that the water was consistently p CO₂ saturated (~90% of the cases) and that the steep terrain favors high gas evasion rates. The mean calculated fluvial export was 5.4 tC·km^?2·year^?1 with inorganic carbon dominating (dissolved inorganic carbon:dissolved organic carbon ratio >4), and degas rates (~40 tC km^?2·year^?1) were nearly sevenfold higher than the downstream export. The homogeneous land use in this nested catchment system results in similar water‐quality characteristics, and therefore, export rates are expected to be closely related to the rainfall–runoff relationships at each scale. Although the sampling campaigns did not fully reproduce storm‐event conditions and related effects such as flushing or dilution of in‐stream carbon, our results indicated a potential link between dissolved inorganic carbon and slower hydrological pathways related to subsurface water storage and movement.     

The impact of storm events on solute exports from a glaciated forested watershed in western New York,USA

This study analysed the importance of precipitation events from May 2003 to April 2004 on surface water chemistry and solute export from a 696 ha glaciated forested watershed in western New York State, USA. The specific objectives of the study were to determine: (a) the temporal patterns of solutes within individual storm events; (b) the impact of precipitation events on seasonal and annual export budgets; and (c) how solute concentrations and loads varied for precipitation events among seasons as functions of storm intensity and antecedent moisture conditions. Analysis of solute trajectories showed that NH₄⁺, total Al and dissolved organic nitrogen (DON) peaked on the hydrograph rising limb, whereas dissolved organic carbon (DOC) concentrations peaked following the discharge peak. Sulphate and base‐cations displayed a dilution pattern with a minimum around peak discharge. End‐member mixing analysis showed that throughfall contributions were highest on the rising limb, whereas valley‐bottom riparian waters peaked following the discharge peak. The trajectories of NO₃^? concentrations varied with season, indicating the influence of biotic processes on the generation, and hence flux, of this solute. Storm events had the greatest impact on the annual budgets for NH₄⁺, K⁺, total dissolved Al, DON and DOC. Storm events during summer had the greatest impact on seasonal solute budgets. Summer events had the highest hourly discharges and high concentrations of solutes. However, NO₃^? and DOC exports during a spring snowmelt event were considerably more than those observed for large events during other periods of the year. Comparisons among storms showed that season, precipitation amount, and antecedent moisture conditions affected solute concentrations and loads. Concentrations of solutes were elevated for storms that occurred after dry antecedent conditions. Seven of the largest storms accounted for only 15% of the annual discharge, but were responsible for 34%, 19%, 64%, 13%, 39% and 24% of the annual exports of NH₄⁺, K⁺, Al, NO₃^?, DON and DOC respectively. These results suggest that the intense and infrequent storms predicted for future climate‐change scenarios will likely increase the exports of solutes like DOC, DON, NH₄⁺, Al and K⁺ from watersheds. Copyright © 2006 John Wiley & Sons, Ltd.     

Seasonal controls on DOC dynamics in nested upland catchments in NE Scotland

Spatial and temporal variability of hydrological responses affecting surface water dissolved organic carbon (DOC) concentrations are important for determining upscaling patterns of DOC export within larger catchments. Annual and intra‐annual variations in DOC concentrations and fluxes were assessed over 2 years at 12 sites (3·40–1837 km²) within the River Dee basin in NE Scotland. Mean annual DOC fluxes, primarily correlated with catchment soil coverage, ranged from 3·41 to 9·48 g m^?2 yr^?1. Periods of seasonal (summer–autumn and winter–spring) DOC concentrations (production) were delineated and related to discharge. Although antecedent temperature mainly determined the timing of switchover between periods of high DOC in the summer‐autumn and low DOC in winter‐spring, inter‐annual variability of export within the same season was largely dependent on its associated water flux. DOC fluxes ranged from 1·39 to 4·80 g m^?2 season^?1 during summer–autumn and 1·43 to 4·15 g m^?2 season^?1 in winter–spring.Relationships between DOC areal fluxes and catchment scale indicated that mainstem fluxes reflect the averaging of highly heterogeneous inputs from contrasting headwater catchments, leading to convergent DOC fluxes at catchment sizes of ca 100 km². However, during summer–autumn periods, in contrast to winter–spring, longitudinal mainstem DOC fluxes continue to decrease, most likely because of increasing biological processes. This highlights the importance of considering seasonal as well as annual changes in DOC fluxes with catchment scale. This study increases our understanding of the temporal variability of DOC upscaling patterns reflecting cumulative changes across different catchment scales and aids modelling of carbon budgets at different stages of riverine systems. Copyright © 2010 John Wiley & Sons, Ltd.     

Relationship of topography to surface water chemistry with particular focus on nitrogen and organic carbon solutes within a forested watershed in Hokkaido,Japan

We studied the relationships between streamwater chemistry and the topography of subcatchments in the Dorokawa watershed in Hokkaido Island, northern Japan, to examine the use of topography as a predictor of streamwater chemistry in a watershed with relatively moderate terrain compared with other regions of Japan. Topographic characteristics of the Dorokawa watershed and its subcatchments were expressed as topographic index (TI) values, which ranged from 4·5 to 20·4 for individual grid cells (50 × 50 m²), but averaged from 6·4 to 7·4 for the 20 subcatchments. Streamwater samples for chemical analyses were collected four times between June and October 2002 from 20 locations in the watershed. The pH of water that passed through the watershed increased from ～5·0 to 7·0, with major increases in Na⁺ and Ca²⁺ and marked decreases in NO₃^? and SO . Distinctive spatial patterns were observed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and NO₃^? concentrations of streamwater across the watershed. Statistical analyses indicated significant linear relationships between the average TI values of subcatchments and DOC, DON, and NO₃^? concentrations. Furthermore, the proportion of DOC in streamwaters in the wet season increased with TI values relative to other nitrogen species, whereas NO₃^? concentrations decreased with TI. The gradients of soil wetness and the presence of wetlands explained many of the observed spatial and temporal patterns of DOC, DON, and NO₃^? concentrations in the surface waters of the Dorokawa watershed. Our results suggest that the TI is especially useful for predicting the spatial distribution of DOC, DON and NO₃^? in the surface waters of Hokkaido, where topographical relief is moderate and wetlands more common than in other regions of Japan. Copyright © 2006 John Wiley & Sons, Ltd.     

Variable nitrate concentration–discharge relationships in a forested watershed

The relationship between solute concentrations and discharge can inform an integrated understanding of hydrological and biogeochemical processes at watershed scales. Recent work from multiple catchments has shown that there is typically little variation in concentration relative to large variations in discharge. This pattern has been described as chemostatic behavior. Pond Branch, a forested headwater catchment in Maryland, has been monitored for stream nitrate (NO₃^?) concentrations at weekly intervals for 14 years. In the growing season and autumn of 2011 a high‐frequency optical NO₃^? sensor was used to supplement the long‐term weekly data. In this watershed, long‐term weekly data show that NO₃^? concentrations decrease with increasing discharge whereas 6 months of 15‐minute sensor observed concentrations reveal a more chemostatic behavior. High‐frequency NO₃^? concentrations from the sensor collected during different storm events reveal variable concentration–discharge patterns highlighting the importance of high resolution data and ecohydrological drivers in controlling solute export for biologically reactive solutes such as NO₃^?.     

Hydrologic and biogeochemical controls on the spatial and temporal patterns of nitrogen and phosphorus in the Kuparuk River,arctic Alaska

Nitrogen (N) and phosphorus (P) dynamics in the Kuparuk River in arctic Alaska were characterized in a 3‐year study using routine samples near the mouth of the river at the Arctic Ocean, synoptic whole‐river surveys, and temporally intense sampling during storms in three headwater basins. The Lower Kuparuk River has low nitrate concentrations (mean [NO₃]‐N] = 17 µg l^?1 ± 1·6 SE) and dissolved inorganic N (DIN, mean [N] = 31 µg l^?1 ± 1·2 SE) compared with rivers in more temperate environments. Organic forms constituted on average 90% of the N exported to the Arctic Ocean, and high ratios of dissolved organic N (DON) to total dissolved N (TDN) concentrations (mean 0·92) likely result from waterlogged soils formed by reduced infiltration due to permafrost and low hydrologic gradients. Annual export of TDN, DON, and particulate N averaged 52 kg km^?2, 48 kg km^?2, and 4·1 kg km^?2 respectively. During snowmelt, the high volume of runoff typically results in the highest nutrient loads of the year, although high discharge during summer storms can result in substantial nutrient loading over short periods of time. Differences in seasonal flow regime (snowmelt versus rain) and storm‐driven variation in discharge appear to be more important for determining nutrient concentrations than is the spatial variation in processes along the transect from headwaters towards the ocean. Both the temporal variation in nitrate:DIN ratios of headwater streams and the spatial variation in nitrate:DIN between larger sub‐basins and smaller headwater catchments is likely controlled by shifts in nitrification and soil anoxia. Copyright © 2008 John Wiley & Sons, Ltd.     

Wetland nitrogen dynamics in an Adirondack forested watershed

Wetlands often form the transition zone between upland soils and watershed streams, however, stream–wetland interactions and hydrobiogeochemical processes are poorly understood. We measured changes in stream nitrogen (N) through one riparian wetland and one beaver meadow in the Archer Creek watershed in the Adirondack Mountains of New York State, USA from 1 March to 31 July 1996. In the riparian wetland we also measured changes in groundwater N. Groundwater N changed significantly from tension lysimeters at the edge of the peatland to piezometer nests within the peatland. Mean N concentrations at the peatland perimeter were 1·5, 0·5 and 18·6 µmol L^?1 for NH₄⁺, NO₃^? and DON (dissolved organic nitrogen), respectively, whereas peatland groundwater N concentration was 56·9, 1·5 and 31·6 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively. The mean concentrations of stream water N species at the inlet to the wetlands were 1·5, 10·1 and 16·9 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively and 1·6, 28·1 and 8·4 µmol L^?1 at the wetland outlet. Although groundwater total dissolved N (TDN) concentrations changed more than stream water TDN through the wetlands, hydrological cross‐sections for the peatland showed that wetland groundwater contributed minimally to stream flow during the study period. Therefore, surface water N chemistry was affected more by in‐stream N transformations than by groundwater N transformations because the in‐stream changes, although small, affected a much greater volume of water. Stream water N input–output budgets indicated that the riparian peatland retained 0·16 mol N ha^?1 day^?1 of total dissolved N and the beaver meadow retained 0·26 mol N ha^?1 day^?1 during the study period. Nitrate dominated surface water TDN flux from the wetlands during the spring whereas DON dominated during the summer. This study demonstrates that although groundwater N changed significantly in the riparian peatland, those changes were not reflected in the stream. Consequently, although in‐stream changes of N concentrations were less marked than those in groundwater, they had a greater effect on stream water chemistry—because wetland groundwater contributed minimally to stream flow. Copyright © 2004 John Wiley & Sons, Ltd.     

On the biogeochemical response of a glacierized High Arctic watershed to climate change: revealing patterns,processes and heterogeneity among micro‐catchments

Our novel study examines landscape biogeochemical evolution following deglaciation and permafrost change in Svalbard by looking at the productivity of various micro‐catchments existing within one watershed. It also sheds light on how moraine, talus and soil environments contribute to solute export from the entire watershed into the downstream marine ecosystem. We find that solute dynamics in different micro‐catchments are sensitive to abiotic factors such as runoff volume, water temperature, geology, geomorphological controls upon hydrological flowpaths and landscape evolution following sea level and glacial changes. Biotic factors influence the anionic composition of runoff because of the importance of microbial SO₄^2? and NO₃^? production. The legacy of glaciation and its impact upon sea level changes is shown to influence local hydrochemistry, allowing Cl^? to be used as a tracer of thawing permafrost that has marine origins. However, we show that a ‘glacial signal’ dominates solute export from the watershed. Therefore, although climatically driven change in the proglacial area has an influence on local ecosystems, the biogeochemical response of the entire watershed is dominated by glacially derived products of rapid chemical weathering. Consequently, only the study of micro‐catchments existing within watersheds can uncover the landscape response to contemporary climate change. Copyright © 2014 John Wiley & Sons, Ltd.     

Dissolved organic matter dynamics during the spring snowmelt at a boreal river valley mire complex in Northwest Russia

Boreal mire landscapes are rich in soil carbon and significantly contribute to the carbon input of aquatic ecosystems. They are composed of different mesoscale ecohydrological subunits, whose individual contributions to the water and carbon export of mire catchments are not well understood. The spring snowmelt period is the major hydrological event in the annual water cycle of the boreal regions and strongly influences the carbon flux between the terrestrial and aquatic systems. The aim of this study was (1) to provide a conceptual understanding of the spatial and temporal dynamics of the surface water chemistry along a swamp forest‐fen‐bog gradient during the snowmelt period, (2) to quantify the exported dissolved organic carbon (DOC) content in the runoff and (3) to identify the ecohydrological landscape unit that contributes most to DOC export during the snowmelt period in a heterogeneous mire complex in Northwest Russia. The highest DOC concentrations were detected in the swamp forest, and the lowest concentrations were observed at the treeless bog by the end of the snowmelt period (swamp forest: 37–43 mg l^?1, bog: 13–17 mg l^?1). During the spring snowmelt period, a significant amount (~1.7 g C m^?2) of DOC was transferred by the ~74 mm of runoff from the catchment into the river. Variability in the thawing periods led to differences in the relative contributions of each ecohydrological zone to the carbon export measured at a stream channel draining the studied part of the mire complex. An increased understanding of the variation in DOC concentrations and contributions from the mesoscale ecohydrological subunits to carbon export can help to predict the potential regional loss of DOC based on land cover type under climate change. Copyright © 2015 John Wiley & Sons, Ltd.     

Response of deep groundwater to land use change in desert basins of the Trans‐Pecos region,Texas, USA: Effects on infiltration,recharge, and nitrogen fluxes

Quantifying the effects of anthropogenic processes on groundwater in arid regions can be complicated by thick unsaturated zones with long transit times. Human activities can alter water and nutrient fluxes, but their impact on groundwater is not always clear. This study of basins in the Trans‐Pecos region of Texas links anthropogenic land use and vegetation change with alterations to unsaturated zone fluxes and regional increases in basin groundwater NO₃^? concentrations. Median increases in groundwater NO₃^? (by 0.7–0.9 mg‐N/l over periods ranging from 10 to 50+ years) occurred despite low precipitation (220–360 mm/year), high potential evapotranspiration (~1570 mm/year), and thick unsaturated zones (10–150+ m). Recent model simulations indicate net infiltration and groundwater recharge can occur beneath Trans‐Pecos basin floors, and may have increased due to irrigation and vegetation change. These processes were investigated further with chemical and isotopic data from groundwater and unsaturated zone cores. Some unsaturated zone solute profiles indicate flushing of natural salt accumulations has occurred. Results are consistent with human‐influenced flushing of naturally accumulated unsaturated zone nitrogen as an important source of NO₃^? to the groundwater. Regional mass balance calculations indicate the mass of natural unsaturated zone NO₃^? (122–910 kg‐N/ha) was sufficient to cause the observed groundwater NO₃^? increases, especially if augmented locally with the addition of fertilizer N. Groundwater NO₃^? trends can be explained by small volumes of high NO₃^? modern recharge mixed with larger volumes of older groundwater in wells. This study illustrates the importance of combining long‐term monitoring and targeted process studies to improve understanding of human impacts on recharge and nutrient cycling in arid regions, which are vulnerable to the effects of climate change and increasing human reliance on dryland ecosystems.     

Factors influencing the release of dissolved organic carbon and dissolved forms of nitrogen from a small upland headwater during autumn runoff events

We identify and assess the relative importance of the principal factors influencing the release of dissolved organic carbon (DOC) and dissolved forms of nitrogen (N) from a small upland headwater dominated by podzolic soils during a sequence of autumn runoff events. We achieve this by subjecting high‐resolution hydrometeorological and hydrochemical data to an R‐mode principal component factor analysis and a stepwise multivariate regression analysis. We find that the release of DOC and N is influenced by four principal factors, namely event magnitude, soil water flow through the Bs horizon, the length of time since the soil profile was last flushed, and rewetting of the H horizon. The release of DOC and dissolved organic nitrogen (DON) is most strongly influenced by the combination of event magnitude and soil water flow through the Bs horizon, and to a lesser extent by the length of time since the soil profile was last flushed. Rewetting of the H horizon also influences the release of DOC, but this is not the case for DON. The release of nitrate (NO₃‐N) is most strongly influenced by the combination of the length of time since the soil profile was last flushed and rewetting of the H horizon, and to a lesser extent by event magnitude. Soil water flow through the Bs horizon does not influence the release of NO₃‐N. We argue that the mechanisms by which the above factors influence the release of DOC and N are probably strongly associated with moisture‐dependent biological activity, which governs the turnover of organic matter in the soil and limits the availability of NO₃‐N in the soil for leaching. We conclude that the release of DOC and N from upland headwaters dominated by podzolic soils is largely controlled by the variable interaction of hydrometeorological factors and moisture‐dependent biological processes, and that a shift in climate towards drier summers and wetter winters may result in the release of DOC and N becoming increasingly variable and more episodic in the future. Copyright © 2006 John Wiley & Sons, Ltd.     

Relating nitrogen export patterns from a mixed land use catchment in NW Spain with rainfall and streamflow

The temporal variability in nitrogen (N) transport in the Corbeira agroforestry catchment (NW Spain) was analysed from October 2004 to September 2008. Nitrate (NO₃–N) and total Kjeldahl nitrogen (TKN) loads and concentrations were determined at various timescales (annual, seasonal and event). The results revealed a strong intra‐annual and inter‐annual variability in N transport influenced by weather patterns and consequently by the hydrological regime. Mean annual export of total N in the catchment was 5.5 kg ha^?1 year^?1, with NO₃–N being the dominant form. Runoff events comprised 10% of the study period but contributed 40 and 61% of the total NO₃–N and TKN loads, respectively. The NO₃–N and TKN concentrations were higher during runoff events than under baseflow conditions, pointing to diffuse sources of N. The mobilization of TKN during runoff events was attributed to surface runoff, while NO₃–N might be related to subsurface and groundwater flow. Runoff events were characterized by high variability in N loads and concentrations. Higher variability was observed in N loads than in N concentrations, indicating that event magnitude plays an important role in N transport in this catchment; event magnitude explained approximately 96% of the NO₃–N load. However, a combination of variables related to runoff event intensity (rainfall, discharge increase and kinetic energy) explained only 66% of the TKN load. Copyright © 2014 John Wiley & Sons, Ltd.     

Water balance,nutrient and carbon export from a heath forest catchment in central Amazonia,Brazil

Carbon storage values in the Amazon basin have been studied through different approaches in the last decades in order to clarify whether the rainforest ecosystem is likely to act as a sink or source for carbon in the near future. This water balance, dissolved organic carbon (DOC) and nutrient export study were carried out in a micro‐scale heath forest (Campina) catchment in central Amazonia, Brazil. For a 1‐year study period (18 March 2007 until 19 March 2008), rainfall amounted to 3054 mm; of which, 1532 mm was evaporated by the forest (4.1 mm day^?1). Rainfall interception loss amounted to 15.6% of gross rainfall. Surface runoff amounted to 485 mm, whereas another 1071 mm was discharged as regional groundwater outflow. Accumulated DOC exports in surface runoff amounted to 15.3 g m^?2 year^?1, whereas the total carbon exported was 55.9 g m^?2. This is much higher than that observed for a nearby tall rainforest catchment in central Amazonia (DOC export < 20 g m^?2). As Campina heath forest areas cover a significant proportion of the Amazon Basin, these differences in ecosystem hydrological carbon exports should be taken into account in future studies assessing the carbon budget for the Amazon Basin. Macro‐nutrient exports were low, but those of calcium and potassium were higher than those observed for tall rainforest in the Amazon, which may be caused by a lower retention capacity of the heath forest ecosystem. Copyright © 2015 John Wiley & Sons, Ltd.     

Using an inverse modelling approach with equifinality control to investigate the dominant controls on snowmelt nutrient export

There is great interest in modelling the export of nitrogen (N) and phosphorus (P) from agricultural fields because of ongoing challenges of eutrophication. However, the use of existing hydrochemistry models can be problematic in cold regions because models frequently employ incomplete or conceptually incorrect representations of the dominant cold regions hydrological processes and are overparameterized, often with insufficient data for validation. Here, a process‐based N model, WINTRA, which is coupled to a physically based cold regions hydrological model, was expanded to simulate P and account for overwinter soil nutrient biochemical cycling. An inverse modelling approach, using this model with consideration of parameter equifinality, was applied to an intensively monitored agricultural basin in Manitoba, Canada, to help identify the main climate, soil, and anthropogenic controls on nutrient export. Consistent with observations, the model results suggest that snow water equivalent, melt rate, snow cover depletion rate, and contributing area for run‐off generation determine the opportunity time and surface area for run‐off–soil interaction. These physical controls have not been addressed in existing models. Results also show that the time lag between the start of snowmelt and the arrival of peak nutrient concentration in run‐off increased with decreasing antecedent soil moisture content, highlighting potential implications of frozen soils on run‐off processes and hydrochemistry. The simulations showed TDP concentration peaks generally arriving earlier than NO₃ but also decreasing faster afterwards, which suggests a significant contribution of plant residue Total dissolved Phosphorus (TDP) to early snowmelt run‐off. Antecedent fall tillage and fertilizer application increased TDP concentrations in spring snowmelt run‐off but did not consistently affect NO₃ run‐off. In this case, the antecedent soil moisture content seemed to have had a dominant effect on overwinter soil N biogeochemical processes such as mineralization, which are often ignored in models. This work demonstrates both the need for better representation of cold regions processes in hydrochemical models and the model improvements that are possible if these are included.     

The role of wetland coverage within the near‐stream zone in predicting of seasonal stream export chemistry from forested headwater catchments

Stream chemistry is often used to infer catchment‐scale biogeochemical processes. However, biogeochemical cycling in the near‐stream zone or hydrologically connected areas may exert a stronger influence on stream chemistry compared with cycling processes occurring in more distal parts of the catchment, particularly in dry seasons and in dry years. In this study, we tested the hypotheses that near‐stream wetland proportion is a better predictor of seasonal (winter, spring, summer, and fall) stream chemistry compared with whole‐catchment averages and that these relationships are stronger in dryer periods with lower hydrologic connectivity. We evaluated relationships between catchment wetland proportion and 16‐year average seasonal flow‐weighted concentrations of both biogeochemically active nutrients, dissolved organic carbon (DOC), nitrate (NO₃‐N), total phosphorus (TP), as well as weathering products, calcium (Ca), magnesium (Mg), at ten headwater (<200 ha) forested catchments in south‐central Ontario, Canada. Wetland proportion across the entire catchment was the best predictor of DOC and TP in all seasons and years, whereas predictions of NO₃‐N concentrations improved when only the proportion of wetland within the near‐stream zone was considered. This was particularly the case during dry years and dry seasons such as summer. In contrast, Ca and Mg showed no relationship with catchment wetland proportion at any scale or in any season. In forested headwater catchments, variable hydrologic connectivity of source areas to streams alters the role of the near‐stream zone environment, particularly during dry periods. The results also suggest that extent of riparian zone control may vary under changing patterns of hydrological connectivity. Predictions of biogeochemically active nutrients, particularly NO₃‐N, can be improved by including near‐stream zone catchment morphology in landscape models.