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.     

Nitrate dynamics in a rural headwater catchment: measurements and modelling

This study was designed to improve our understanding of, and mechanistically simulate, nitrate (NO₃) dynamics in a steep 9.8 ha rural headwater catchment, including its production in soil and delivery to a stream via surface and subsurface processes. A two‐dimensional modelling approach was evaluated for (1) integrating these processes at a hillslope scale annually and within storms, (2) estimating denitrification, and (3) running virtual experiments to generate insights and hypotheses about using trees in streamside management zones (SMZs) to mitigate NO₃ delivery to streams. Total flow was mathematically separated into quick‐ and slow‐flow components; the latter was routed through the HYDRUS software with a nitrogen module designed for constructed wetlands. Flow was monitored for two years. High surface‐soil NO₃ concentrations started to be delivered to the stream via preferential subsurface flow within two days of the storm commencing. Groundwater NO₃‐N concentrations decreased from 1.0 to less than 0.1 mg l^?1 from up‐slope to down‐slope water tables, respectively, which was attributed to denitrification. Measurements were consistent with the flushing of NO₃ mainly laterally from surface soil during and following each storm. The model accurately accounted for NO₃ turnover, leading to the hypotheses that denitrification was a minor flux (<3 kg N ha^?1) compared to uptake (98^?127 kg N ha^?1), and that SMZ trees would reduce denitrification if they lowered the water table. This research provides an example of the measurement and modelling of NO₃ dynamics at a small‐catchment scale with high spatial and temporal resolution. Copyright © 2013 John Wiley & Sons, Ltd.     

Beaver dams along an agricultural stream in southern Ontario,Canada: their impact on riparian zone hydrology and nitrogen chemistry

The hydrology and nitrogen biogeochemistry of a riparian zone were compared before and after the construction of beaver dams along an agricultural stream in southern Ontario, Canada. The beaver dams increased surface flooding and raised the riparian water table by up to 1·0 m. Increased hydraulic gradients inland from the stream limited the entry of oxic nitrate‐rich subsurface water from adjacent cropland. Permeable riparian sediments overlying dense till remained saturated during the summer and autumn months, whereas before dam construction a large area of the riparian zone was unsaturated in these seasons each year. Beaver dam construction produced significant changes in riparian groundwater chemistry. Median dissolved oxygen concentrations were lower in riparian groundwater after dam construction (0·9–2·1 mg L^?1) than in the pre‐dam period (2·3–3·9 mg L^?1). Median NO₃‐N concentrations in autumn and spring were also lower in the post‐dam (0·03–0·07 mg L^?1) versus the pre‐dam period (0·1–0·3 mg L^?1). In contrast, median NH₄‐N concentrations in autumn and spring months were higher after dam construction (0·3–0·4 mg L^?1) than before construction (0·13–0·14 mg L^?1). Results suggest that beaver dams can increase stream inflow to riparian areas that limit water table declines and increase depths of saturated riparian soils which become more anaerobic. These changes in subsurface hydrology and chemistry have the potential to affect the transport and transformation of nitrate fluxes from adjacent cropland in agricultural landscapes. Copyright © 2009 John Wiley & Sons, Ltd.     

The impact of pipe flow in riparian peat deposits on nitrate transport and removal

The effect of preferential flow in soil pipes on nitrate retention in riparian zones is poorly understood. The characteristics of soil pipes and their influence on patterns of groundwater transport and nitrate dynamics were studied along four transects in a 1‐ to >3‐m deep layer of peat and marl overlying an oxic sand aquifer in a riparian zone in southern Ontario, Canada. The peat‐marl deposit, which consisted of several horizontal layers with large differences in bulk density, contained soil pipes that were generally 0.1 to 0.2 m in diameter and often extended vertically for 1 to >2 m. Springs that produced overland flow across the riparian area occurred at some sites where pipes extended to the peat surface. Concentrations of NO₃^?–N (20–30 mg L^?1) and dissolved oxygen (DO) (4–6 mg L^?1) observed in peat pipe systems and surface springs were similar to values in the underlying sand aquifer, indicating that preferential flow transported groundwater with limited nitrate depletion. Low NO₃^?–N concentrations of <5 mg L^?1 and enriched δ¹⁵N values indicated that denitrification was restricted to small areas of the peat where pipes were absent. Groundwater DO concentrations declined rapidly to <2 mg L^?1 in the peat matrix adjacent to pipes, whereas high NO₃^?–N concentrations of >15 mg L^?1 extended over a larger zone. Low dissolved organic carbon values at these locations suggest that supplies of organic carbon were not sufficient to support high rates of denitrification, despite low DO conditions. These data indicate that it is important to develop a greater understanding of pipes in peat deposits, which function as sites where the transport of large fluxes of water with low biogeochemical reaction rates can limit the nitrate removal capacity of riparian zones. Copyright © 2011 John Wiley & Sons, Ltd.     

Mobility of major ions and nutrients in the unsaturated zone during paddy cultivation: a field study and solute transport modelling approach

Study of the movement of water and solute within soil profiles is important for a number of reasons. Accumulation of prominent contaminants from agricultural chemicals in the unsaturated zone over the years is a major concern in many parts of the world. As a result, the unsaturated zone has been a subject of great research interest during the past decade. Hence, an intensive field study was conducted in a part of Palar and Cheyyar river basins to understand the variation of major ions and nutrients in the soil zone during paddy cultivation. The chloride and nitrate data were used to model the movement of these chemicals in the unsaturated zone using the HYDRUS‐2D model. The field study shows that fertilizer application and irrigation return flow increases the major ions and nutrients concentration in the unsaturated zone. Further, the nutrient concentrations are regulated by plant uptake, fertilizer application and infiltration rate. Additionally, denitrification and soil mineralization processes also regulate the nitrogen concentration in the unsaturated zone. The solute transport modelling study concluded that the simulated results match reasonably with the observed trends. Simulated concentrations of chloride and nitrate for a 5‐year period indicate that the concentrations of these ions fluctuate in a cyclic manner (from 60 to 68 mg l^?1 and from 3·4 to 3·5 mg l^?1 respectively in groundwater) with no upward and downward trend. The influence of excessive fertilizer application on groundwater was also modelled. The model predicts an increase of about 17 mg l^?1 of chloride and 2·3 mg l^?1 of nitrogen in the groundwater of this area when the application of fertilizers is doubled. The model indicates that the present level of use of agrochemicals is no threat to the groundwater quality. Copyright © 2007 John Wiley & Sons, Ltd.     

Hydrological heterogeneity of an alpine stream–lake network in Switzerland

Water source and lake landscape position can strongly influence the physico‐chemical characteristics of flowing waters over space and time. We examined the physico‐chemical heterogeneity in surface waters of an alpine stream‐lake network (>2600 m a.s.l.) in Switzerland. The catchment comprises two basins interspersed with 26 cirque lakes. The larger lakes in each basin are interconnected by streams that converge in a lowermost lake with an outlet stream. The north basin is primarily fed by precipitation and groundwater, whereas the south basin is fed mostly by glacial melt from rock glaciers. Surface flow of the entire channel network contracted by ～60% in early autumn, when snowmelt runoff ceased and cold temperatures reduced glacial outputs, particularly in the south basin. Average water temperatures were ～4 °C cooler in the south basin, and temperatures increased by about 4–6 °C along the longitudinal gradient within each basin. Although overall water conductivity was low (<27 µS cm^?1) because of bedrock geology (ortho‐gneiss), the south basin had two times higher conductivity values than the north basin. Phosphate‐phosphorus levels were below analytical detection limits, but particulate phosphorus was about four times higher in the north basin (seasonal average: 9 µg l^?1) than in the south basin (seasonal average: 2 µg l^?1). Dissolved nitrogen constituents were around two times higher in the south basin than in the north basin, with highest values averaging > 300 µg l^?1 (nitrite + nitrate‐nitrogen), whereas particulate nitrogen was approximately nine times greater in the north basin (seasonal average: 97 µg l^?1) than in the south basin (seasonal average: 12 µg l^?1). Total inorganic carbon was low (usually <0·8 mg l^?1), silica was sufficient for algal growth, and particulate organic carbon was 4·5 times higher in the north basin (average: 0·9 mg l^?1) than in the south basin (average: 0·2 mg l^?1). North‐basin streams showed strong seasonality in turbidity, particulate‐nitrogen and ‐phosphorus, and particulate organic carbon, whereas strong seasonality in south‐basin streams was observed in conductivity and dissolved nitrogen. Lake position influenced the seasonal dynamics in stream temperatures and nutrients, particularly in the groundwater/precipitation‐fed north‐basin network. Copyright © 2007 John Wiley & Sons, Ltd.     

Travel time controls the magnitude of nitrate discharge in groundwater bypassing the riparian zone to a stream on Virginia's coastal plain

Groundwater that bypasses the riparian zone by travelling along deep flow paths may deliver high concentrations of fertilizer‐derived NO₃^? to streams, or it may be impacted by the NO₃^? removal process of denitrification in streambed sediments. In a study of a small agricultural catchment on the Atlantic coastal plain of Virginia's eastern shore, we used seepage meters deployed in the streambed to measure specific discharge of groundwater and its solute concentrations for various locations and dates. We used values of Cl^? concentration to discriminate between bypass water recharged distal to the stream and that contained high NO₃^? but low Cl^? concentrations and riparian‐influenced water recharged proximal to the stream that contained low NO₃^? and high Cl^? concentrations. The travel time required for bypass water to transit the 30‐cm‐thick, microbially active denitrifying zone in the streambed determined the extent of NO₃^? removal, and hydraulic conductivity determined travel time through the streambed sediments. At all travel times greater than 2 days, NO₃^? removal was virtually complete. Comparison of the timescales for reaction and transport through the streambed sediments in this system confirmed that the predominant control on nitrate flux was travel time rather than denitrification rate coefficients. We conclude that extensive denitrification can occur in groundwater that bypasses the riparian zone, but a residence time in biologically active streambed sediments sufficient to remove a large fraction of the NO₃^? is only achieved in relatively low‐conductivity porous media. Instead of viewing them as separate, the streambed and riparian zone should be considered an integrated NO₃^? removal unit. Copyright © 2011 John Wiley & Sons, Ltd.     

The role of perched aquifers in hydrological connectivity and biogeochemical processes in vernal pool landscapes,Central Valley,California

Relatively little is known about the role of perched aquifers in hydrological, biogeochemical, and biological processes of vernal pool landscapes. The objectives of this study are to introduce a perched aquifer concept for vernal pool formation and maintenance and to examine the resulting hydrological and biogeochemical phenomena in a representative catchment with three vernal pools connected to one another and to a seasonal stream by swales. A combined hydrometric and geochemical approach was used. Annual rainfall infiltrated but perched on a claypan/duripan, and this perched groundwater flowed downgradient toward the seasonal stream. The upper layer of soil above the claypan/duripan is ～0·6 m in thickness in the uplands and ～0·1 m in thickness in the vernal pools. Some groundwater flowed through the vernal pools when heads in the perched aquifer exceeded ～0·1 m above the claypan/duripan. Perched groundwater discharge accounted for 30–60% of the inflow to the vernal pools during and immediately following storm events. However, most perched groundwater flowed under or around the vernal pools or was recharged by annual rainfall downgradient of the vernal pools. Most of the perched groundwater was discharged to the outlet swale immediately upgradient of the seasonal stream, and most water discharging from the outlet swale to the seasonal stream was perched groundwater that had not flowed through the vernal pools. Therefore, nitrate‐nitrogen concentrations were lower (e.g. 0·17 to 0·39 mg l^?1) and dissolved organic carbon concentrations were higher (e.g. 5·97 to 3·24 mg l^?1) in vernal pool water than in outlet swale water discharging to the seasonal stream. Though the uplands, vernal pools, and seasonal stream are part of a single surface‐water and perched groundwater system, the vernal pools apparently play a limited role in controlling landscape‐scale water quality. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydrological flow paths controlling stream chemistry in Japanese forested watersheds

Water sources and flow paths contributing to stream chemistry were evaluated in four Japanese forested watersheds with steep topography (slopes ≥30°). Stream chemistry during periods without rainfall and during events with less than 100 mm of precipitation was similar to seepage water chemistry, but markedly different from that of soil water which had higher concentrations of NO⁻₃ and Ca²⁺ and lower concentrations of Na⁺ and HCO⁻₃. Also, stream Cl⁻ concentrations in a Cl⁻‐treated watershed did not increase either during events with less than 100 mm of total rainfall or at baseflow conditions, even three years after the Cl⁻ treatment. These results suggest that groundwater within bedrock fissures of Paleozoic strata had a long residence time and was a major contributor to steam water under baseflow conditions and even during small precipitation events (≤100 mm). In contrast, for large precipitation events (≥100 mm), stream chemistry became more similar to soil water chemistry, especially within the steepest watershed. Also, for large precipitation events, stream Cl⁻ concentrations in the Cl⁻‐treated watershed increased markedly. These results suggest that soil water was a major contributor to stream waters only during these large events. Copyright © 1999 John Wiley & Sons, Ltd.     

Hydrological flowpaths and nitrate removal rates within a riparian floodplain along a fourth‐order stream in Brittany (France)

Three main reservoirs were identified that contribute to the shallow subsurface flow regime of a valley drained by a fourth‐order stream in Brittany (western France). (i) An upland flow that supplied a wetland area, mainly during the high‐water period. It has high N‐NO₃^? and average Cl^? concentrations. (ii) A deep confined aquifer characterized by low nitrate and low chloride concentrations that supplied the floodplain via flow upwelling. (iii) An unconfined aquifer under the riparian zone with high Cl^? and low N‐NO₃^? concentrations where biological processes removed groundwater nitrate. This aquifer collected the upland flow and supplied a relict channel that controlled drainage from the whole riparian zone. Patterns of N‐NO₃^? and Cl^? concentrations along riparian transects, together with calculated high nitrate removal, indicate that removal occurred mainly at the hillslope–riparian zone interface (i.e. first few metres of wetland), whereas dilution occurred in lower parts of the transects, especially during low‐water periods and at the beginning of recharge periods. Stream flow was modelled as a mixture of water from the three reservoirs. An estimation of these contributions revealed that the deep aquifer contribution to stream flow averaged 37% throughout the study period, while the contribution of the unconfined reservoir below the riparian zone and hillslope flow was more variable (from ca 6 to 85%) relative to rainfall events and the level of the riparian water table. At the entire riparian zone scale, NO₃^? removal (probably from denitrification) appeared most effective in winter, despite higher estimated upland NO₃^? fluxes entering the riparian zone during this period. Copyright © 2003 John Wiley & Sons, Ltd.     

Variations in dissolved CO2 and CH4 in a first‐order stream and catchment: an investigation of soil–stream linkages

Spatial and seasonal variations in CO₂ and CH₄ concentrations in streamwater and adjacent soils were studied at three sites on Brocky Burn, a headwater stream draining a peatland catchment in upland Britain. Concentrations of both gases in the soil atmosphere were significantly higher in peat and riparian soils than in mineral soils. Peat and riparian soil CO₂ concentrations varied seasonally, showing a positive correlation with air and soil temperature. Streamwater CO₂ concentrations at the upper sampling site, which mostly drained deep peats, varied from 2·8 to 9·8 mg l^?1 (2·5 to 11·9 times atmospheric saturation) and decreased markedly downstream. Temperature‐related seasonal variations in peat and riparian soil CO₂ were reflected in the stream at the upper site, where 77% of biweekly variation was explained by an autoregressive model based on: (i) a negative log‐linear relationship with stream flow; (ii) a positive linear relationship with soil CO₂ concentrations in the shallow riparian wells; and (iii) a negative linear relationship with soil CO₂ concentrations in the shallow peat wells, with a significant 2‐week lag term. These relationships changed markedly downstream, with an apparent decrease in the soil–stream linkage and a switch to a positive relationship between stream flow and stream CO₂. Streamwater CH₄ concentrations also declined sharply downstream, but were much lower (<0·01 to 0·12 mg l^?1) than those of CO₂ and showed no seasonal variation, nor any relationship with soil atmospheric CH₄ concentrations. However, stream CH₄ was significantly correlated with stream flow at the upper site, which explained 57% of biweekly variations in dissolved concentrations. We conclude that stream CO₂ can be a useful integrative measure of whole catchment respiration, but only at sites where the soil–stream linkage is strong. Copyright © 2004 John Wiley & Sons, Ltd.     

High chloride concentrations in the soil and groundwater under an oak hedge in the West of France: an indicator of evapotranspiration and water movement

Chloride is a major anion in soil water and its concentration rises essentially as a function of evapotranspiration. Compared to herbaceous vegetation, high transpiration rates are measured for isolated trees, shelterbelts or hedgerows. This article deals with the influence of a tree hedge on the soil and groundwater Cl^? concentrations and the possibility of using Cl^? as an indicator of transpiration and water movements near the tree rows. Cl^? concentrations were measured over 1 year at different depths in the unsaturated zone and in the groundwater along a transect intersecting a bottomland oak hedge. We observed a strong spatial heterogeneity of Cl^? concentrations, with very high values up to 2 g l^?1 in the unsaturated zone and 1·2 g l^?1 in the upper part of the groundwater. This contrasts with the low and homogeneous concentrations (60–70 mg l^?1) in the deeper part of the groundwater. Cl^? accumulation in the unsaturated zone at the end of the vegetation season allows us to identify the active root zone extension of trees. In winter, upslope of the tree row, downwards leaching partly renews the soil solution in the root zone, while the slow water movement under the trees or farther downslope results in Cl^? accumulation and leads to a salinization of the soil and groundwater. This salinization is of the same order as experimental conditions produce negative effects on oak seedlings. The measurement of Cl^? concentrations in the unsaturated zone under tree rows at the end of the vegetation season would indicate whether certain topographic, pedological or climatic conditions are likely to favour a strong salinization of the soil, as observed in the present study. Copyright © 2009 John Wiley & Sons, Ltd.     

Contributions of bedrock groundwater to the upscaling of storm‐runoff generation processes in weathered granitic headwater catchments

We examined the contributions of bedrock groundwater to the upscaling of storm‐runoff generation processes in weathered granitic headwater catchments by conducting detailed hydrochemical observations in five catchments that ranged from zero to second order. End‐member mixing analysis (EMMA) was performed to identify the geographical sources of stream water. Throughfall, hillslope groundwater, shallow bedrock groundwater, and deep bedrock groundwater were identified as end members. The contribution of each end member to storm runoff differed among the catchments because of the differing quantities of riparian groundwater, which was recharged by the bedrock groundwater prior to rainfall events. Among the five catchments, the contribution of throughfall was highest during both baseflow and storm flow in a zero‐order catchment with little contribution from the bedrock groundwater to the riparian reservoir. In zero‐order catchments with some contribution from bedrock groundwater, stream water was dominated by shallow bedrock groundwater during baseflow, but it was significantly influenced by hillslope groundwater during storms. In the first‐order catchment, stream water was dominated by shallow bedrock groundwater during storms as well as baseflow periods. In the second‐order catchment, deeper bedrock groundwater than that found in the zero‐order and first‐order catchments contributed to stream water in all periods, except during large storm events. These results suggest that bedrock groundwater influences the upscaling of storm‐runoff generation processes by affecting the linkages of geomorphic units such as hillslopes, riparian zones, and stream channels. Our results highlight the need for a three‐dimensional approach that considers bedrock groundwater flow when studying the upscaling of storm‐runoff generation processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Geologic controls on the chemical behaviour of nitrate in riverside alluvial aquifers,Korea

To investigate the origin and behaviour of nitrate in alluvial aquifers adjacent to Nakdong River, Korea, we chose two representative sites (Wolha and Yongdang) having similar land‐use characteristics but different geology. A total of 96 shallow groundwater samples were collected from irrigation and domestic wells tapping alluvial aquifers. About 63% of the samples analysed had nitrate concentrations that exceeded the Korean drinking water limit (44·3 mg l^?1 NO₃^?), and about 35% of the samples had nitrate concentrations that exceeded the Korean groundwater quality standard for agricultural use (88·6 mg l^?1 NO₃^?). Based on nitrogen isotope analysis, two major nitrate sources were identified: synthetic fertilizer (about 4‰ δ¹⁵N) applied to farmland, and animal manure and sewage (15–20‰ δ¹⁵N) originating from upstream residential areas. Shallow groundwater in the farmland generally had higher nitrate concentrations than those in residential areas, due to the influence of synthetic fertilizer. Nitrate concentrations at both study sites were highest near the water table and then progressively decreased with depth. Nitrate concentrations are also closely related to the geologic characteristics of the aquifer. In Yongdang, denitrification is important in regulating nitrate chemistry because of the availability of organic carbon from a silt layer (about 20 m thick) below a thin, sandy surface aquifer. In Wolha, however, conservative mixing between farmland‐recharged water and water coming from a village is suggested as the dominant process. Mixing ratios estimated based on the nitrate concentrations and the δ¹⁵N values indicate that water originating from the village affects the nitrate chemistry of the shallow groundwater underneath the farmland to a large extent. Copyright © 2003 John Wiley & Sons, Ltd.     

How important is groundwater availability and stream perenniality to riparian and floodplain tree growth?

Riparian vegetation is important for stream functioning and as a major landscape feature. For many riparian plants, shallow groundwater is an important source of water, particularly in areas where rainfall is low, either annually or seasonally, and when extended dry conditions prevail for all or part of the year. The nature of tree water relationships is highly complex. Therefore, we used multiple lines of evidence to determine the water sources used by the dominant tree species Eucalyptus camaldulensis (river red gum), growing in riparian and floodplain areas with varying depth to groundwater and stream perenniality. Dendrometer bands were used to measure diel, seasonal, and annual patterns of tree water use and growth. Water stable isotopes (δ²H and δ¹⁸O) in plant xylem, soil water, and groundwater were measured to determine spatial and temporal patterns in plant water source use. Our results indicated riparian trees located on relatively shallow groundwater had greater growth rates, larger diel responses in stem diameter, and were less reactive to extended dry periods, than trees in areas of deep groundwater. These results were supported by isotope analysis that suggested all trees used groundwater when soil water stores were depleted at the end of the dry season, and this was most pronounced for trees with shallow groundwater. Trees may experience more frequent periods of water deficit stress and undergo reduced productivity in scenarios where water table accessibility is reduced, such as drawdown from groundwater pumping activities or periods of reduced rainfall recharge. The ability of trees to adapt to changing groundwater conditions may depend on the speed of change, the local hydrologic and soil conditions as well as the species involved. Our results suggest that E. camaldulesis growing at our study site is capable of utilizing groundwater even to depths >10 m, and stream perenniality is likely to be a useful indicator of riparian tree use of groundwater.     

Run‐off formation in a humid,temperate headwater catchment using a combined hydrological,hydrochemical and isotopic approach (Jizera Mountains,Czech Republic)

The formation of baseflow and stormflow was examined in the 1.18 km² part of the headwater catchment Uhlí?ská, Jizera Mountains, Czech Republic, over the period 2007–2011, by means of run‐off data and environmental tracers ¹⁸O and SiO₂. The baseflow, computed using the digital filter approach BFLOW, contributes 67% to total streamflow and has a mean residence time of 12.3 months. It is formed by groundwater discharge from the valley deluviofluvial granitic sediments, in combination with soil water in weathered layers on hillslopes during rainfall and snowmelt periods. The prevailing source of the groundwater is the infiltration of snowmelt water. Analysis of 20 run‐off events and their hysteretic patterns demonstrated that the stormflow water has a residence time of about 4 months and is generated by preferential flow on hillslopes combined by soil matrix drainage. Because of slower flow in the soil matrix, the enrichment of pore water in SiO₂ is more pronounced. The stormflow and snowmelt water flowing via preferential pathways of upslope minerals soils pushes the pre‐event groundwater through the pathways in wetlands to the stream, and the wetland can be therefore considered as groundwater supplied. This mechanism has been found to be typical for the groundwater‐supplied headwater catchments of the Jizera Mountains and can be also assumed in other mountainous headwaters of the granitic massif in Central Europe. The main methodological contribution of this study are the residence time calculations stratified by baseflow and event flow, identifying run‐off components of different travel times to streams and linking them with geochemical run‐off sources. This achievement was possible because of a comprehensive dataset on hydrology, stable isotopes and silica hydrochemistry in all relevant run‐off generation components. This concept indicates that a possible long‐term change in snowmelt may affect the run‐off regime of headwater catchments to climate or land‐use changes. Copyright © 2013 John Wiley & Sons, Ltd.     

Heavy metal concentrations during storm events in a rehabilitated industrialized catchment

Water quality data collected on a fortnightly or monthly basis are inadequate for assessment and modelling of many water quality problems as storm event samples are underrepresented or missed. This paper examines the stormflow dynamics of heavy metals (Pb, Cu, Cd and Zn) in the Nant‐y‐Fendrod stream, South Wales, which has been affected by 250 years of metal smelting, followed by 35 years of landscape rehabilitation measures. For storm events of contrasting (very dry and very wet) antecedent conditions in May 2000 and February 2001, respectively, temporal changes in streamwater heavy metal concentrations above and below an in‐line flood detention lake are analysed. At the upstream site, peaks in total metal concentration were recorded on the rising limb for Pb (0·150 mg l^?1) and Cu (0·038 mg l^?1) but on the falling limb for Zn (1·660 mg l^?1) and Cd (0·006 mg l^?1) in the summer 2000 storm event, yielding clockwise and anticlockwise hysteretic loops respectively. In contrast, metal concentrations, although high throughout the winter storm event, were diluted somewhat during the storm peak itself. The Pb and Cu appear to be supplied by quickflow processes and transported in close association with fine sediment, whereas Zn and Cd are delivered to the channel and lake by slower subsurface seepage in dissolved form. In the winter 2001 event, antecedent soil moisture and shallow groundwater levels were anomalously high and seepage sources of dissolved metals dominated. Downstream of the lake, Pb and Cu levels and suspended sediment were high in the summer storm, but low in the winter storm, suggesting retention with deposition of fine sediment in the lake during the latter. In the winter storm, Zn and Cd levels were higher downstream than upstream of the lake, perhaps because of additional seepage inputs from the surrounding slopes, which failed to have an impact during summer. An understanding of the complex interplay of antecedent soil moisture and the dynamics of subsurface seepage pathways in relation to the three‐dimensional distribution of sources is important in modelling heavy metal fluxes and levels in contaminated urban catchments. Copyright © 2003 John Wiley & Sons, Ltd.     

Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

Quantifying nitrogen cycling beneath a meander of a low gradient,N‐impacted,agricultural stream using tracers and numerical modelling

In watersheds impacted by nitrate from agricultural fertilizers, nitrification and denitrification may be decoupled as denitrification in the hyporheic zone is not limited to naturally produced nitrate. While most hyporheic research focuses on the 1–2 m of sediment beneath the stream bed, there are a limited number of studies that quantify nitrogen (N) cycling at larger hyporheic scales (10s of metres to kms). We conducted an investigation to quantify N cycling through a single meander of a low gradient, meandering stream, draining an agricultural watershed. Chemistry (major ions and N species) and hydrologic data were collected from the stream and groundwater beneath the meander. Evidence indicates that nearly all the shallow groundwater flowing beneath the meander originates as stream water on the upgradient side of the meander, and returns to the stream on the downgradient side. We quantified the flux of water beneath the meander using a numerical model. The flux of N into and out of the meander was quantified by multiplying the concentration of the important N species (nitrate, ammonium, dissolved organic nitrogen (DON)) by the modelled water fluxes. The flux of N into the meander is dominated by nitrate, and the flux of N out of the meander is dominated by ammonium and DON. While stream nitrate varied seasonally, ammonium and DON beneath the meander were relatively constant throughout the year. When stream nitrate concentrations are high (>2 mg litre^?1), flow beneath the meander is a net sink for N as more N from nitrate in stream water is consumed than is produced as ammonium and DON. When stream nitrate concentrations are low (<2 mg litre^?1), the flux of N entering is less than exiting the meander. On an annual basis, the meander hyporheic flow serves as a net sink for N. Copyright © 2007 John Wiley & Sons, Ltd.     

Groundwater contributions of flow and nitrogen in a headwater agricultural watershed

Nonpoint sources of nitrogen (N) and other nutrients are a major source of water pollution within the Chesapeake Bay watershed and other basins around the world. Human activities associated with agricultural practices can account for a large percentage of N loadings delivered to streams and rivers. This work aims to improve understanding of N transport from groundwater to surface waters, quantifying the principal hydrological processes driving water and N fluxes into and out of a headwater agricultural stream reach. The study site is a 175-m stream reach in a heavily cultivated 40-ha watershed in east-central Pennsylvania. This subwatershed is underlain by fractured shale bedrock, and receives most of its baseflow from groundwater, either by diffuse matrix discharge through the streambed or by localized discharge through riparian seeps. Samples of stream, seep, and shallow groundwater were collected approximately monthly under steady hydrologic conditions in 2017. Calculated matrix flow from hydraulic head and conductivity measurements paired with differential stream gauging was used to solve for the riparian seep flux using a mass balance approach. Riparian seep fluxes ranged from 45 to 217 m³/d, transporting 0.6–4.2 kg N d⁻¹ of nitrate-N from the fractured bedrock aquifer to the stream. Hydrochemical data suggest that the stream is mainly disconnected from the underlying aquifer and that seeps supply essentially all water and N to the system. Seeps are likely sourced with N in nearby agricultural fields and accelerated through the system with shorter residence times than shallow groundwater. Water isotope data reinforced this notion. This study underscores the importance of agriculture as a source of N to ground and surface waters. Identifying source areas that are causing groundwater enrichment of N and seep areas where N discharges to streams is beneficial for developing N pollution mitigation strategies and implementing management practices that aim to reduce nutrient loads to the Chesapeake Bay.