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.     

Nitrate attenuation in soil and shallow groundwater under a bottomland hedgerow in a European farming landscape

In many agricultural areas, hedgerows give rise to strong expectations of reducing the inputs of excess nitrate to the groundwater and rivers. This study aims to analyse the spatial and seasonal influences of a hedgerow on nitrate dynamics in the soil and groundwater. Nitrate (NO₃^?) and chloride (Cl^?) concentrations were measured with spatially dense sampling in the unsaturated soil and in the groundwater along a transect intersecting a bottomland oak (Quercus rubor) hedgerow after the growing season and during the dormant season. We explain NO₃^? dynamics by using Cl^? as an index of tree‐root extension and water transfer. At the end of the growing season, NO₃^? is entirely absorbed by the trees over a large and deep volume corresponding to the rooting zone, where, in contrast Cl^? is highly concentrated due to root exclusion. However, these observed patterns in the soil have no influence on the deep groundwater composition at this season. During the dormant season, water transfer processes feeding the shallow groundwater layer are different upslope and downslope from the hedgerow in relation to the thickness of the unsaturated zone. Upslope, the shallow groundwater is fed by rainwater infiltration through the soil which favours Cl^? dilution. Right under the hedge and downslope, the rapid ascent of the groundwater near the ground surface prevents rainwater input and Cl^? dilution. Under the hedgerow the highest concentrations of Cl^? coincide with the absence of NO₃^? in the shallow groundwater layer and with high concentrations of dissolved organic carbon. The absence of NO₃^? during the dormant season seems to be due to denitrification in the hedgerow rooting zone when it is rapidly saturated by groundwater. Copyright © 2011 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.     

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.     

Impact of redox and transport processes in a riparian wetland on stream water quality in the Fichtelgebirge region,southern Germany

Biologically mediated redox processes in the riparian zone, like denitrification, can have substantially beneficial impacts on stream water quality. The extent of these effects, however, depends greatly on the hydrological boundary conditions. The impact of hydrological processes on a wetland's nitrogen sink capacity was investigated in a forested riparian fen which is drained by a first‐order perennial stream. Here, we analysed the frequency distributions and time‐series of pH and nitrogen, silica, organic carbon and oxygen concentrations in throughfall, soil solution, groundwater and stream water, and the groundwater levels and stream discharges from a 3‐year period. During baseflow conditions, the stream was fed by discharging shallow, anoxic groundwater and by deep, oxic groundwater. Whereas the latter delivered considerable amounts of nitrogen (～0·37 mg l^?1) to the stream, the former was almost entirely depleted of nitrogen. During stormflow, near‐surface runoff in the upper 30 cm soil layer bypassed the denitrifying zone and added significant amounts to the nitrogen load of the stream. Nitrate‐nitrogen was close to 100% of deep groundwater and stream‐water nitrogen concentration. Stream‐water baseflow concentrations of nitrate, dissolved carbon and silica were about 1·6 mg l^?1, 4 mg l^?1 and 7·5 mg l^?1 respectively, and >3 mg l^?1, >10 mg l^?1 and <4 mg l^?1 respectively during discharge peaks. In addition to that macroscale bypassing effect, there was evidence for a corresponding microscale effect: Shallow groundwater sampled by soil suction cups indicated complete denitrification and lacked any seasonal signal of solute concentration, which was in contrast to piezometer samples from the same depth. Moreover, mean solute concentration in the piezometer samples resembled more that of suction‐cup samples from shallower depth than that of the same depth. We conclude that the soil solution cups sampled to a large extent the immobile soil‐water fraction. In contrast, the mobile fraction that was sampled by the piezometers exhibited substantially shorter residence time, thus being less exposed to denitrification, but predominating discharge of that layer to the stream. Consequently, assessing the nitrogen budget based on suction‐cup data tended to overestimate the nitrogen consumption in the riparian wetland. These effects are likely to become more important with the increased frequency and intensity of rainstorms that are expected due to climate change. Copyright © 2006 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.     

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.     

Natural Attenuation of Perchlorate in Denitrified Groundwater

Monitoring of a well‐defined septic system groundwater plume and groundwater discharging to two urban streams located in southern Ontario, Canada, provided evidence of natural attenuation of background low level (ng/L) perchlorate (ClO₄^?) under denitrifying conditions in the field. The septic system site at Long Point contains ClO₄^? from a mix of waste water, atmospheric deposition, and periodic use of fireworks, while the nitrate plume indicates active denitrification. Plume nitrate (NO₃^?‐N) concentrations of up to 103 mg/L declined with depth and downgradient of the tile bed due to denitrification and anammox activity, and the plume was almost completely denitrified beyond 35 m from the tile bed. The ClO₄^? natural attenuation occurs at the site only when NO₃^?‐N concentrations are <0.3 mg/L, after which ClO₄^? concentrations decline abruptly from 187 ± 202 to 11 ± 15 ng/L. A similar pattern between NO₃^?‐N and ClO₄^? was found in groundwater discharging to the two urban streams. These findings suggest that natural attenuation (i.e., biodegradation) of ClO₄^? may be commonplace in denitrified aquifers with appropriate electron donors present, and thus, should be considered as a remediation option for ClO₄^? contaminated groundwater.     

Residence time control on hot moments of net nitrate production and uptake in the hyporheic zone

The retention capacity for biologically available nitrogen within streams can be influenced by dynamic hyporheic zone exchange, a process that may act as either a net source or net sink of dissolved nitrogen. Over 5 weeks, nine vertical profiles of streambed chemistry (NO₃^? and NH₄⁺) were collected above two beaver dams along with continuous high‐resolution vertical hyporheic flux data. The results indicate a non‐linear relation of net NO₃^? production followed by net uptake in the hyporheic zone as a function of residence time. This Lagrangian‐based relation is consistent through time and across varied morphology (bars, pools, glides) above the dams, even though biogeochemical and environmental factors varied. The empirical continuum between net NO₃^? production and uptake and residence time is useful for identifying two crucial residence time thresholds: the transition to anaerobic respiration, which corresponds to the time of peak net nitrate production, and the net sink threshold, which is defined by a net uptake in NO₃^? relative to streamwater. Short‐term hyporheic residence time variability at specific locations creates hot moments of net production and uptake, enhancing NO₃^? production as residence times approach the anaerobic threshold, and changing zones of net NO₃^? production to uptake as residence times increase past the net sink threshold. The anaerobic and net sink thresholds for beaver‐influenced streambed morphology occur at much shorter residence times (1.3 h and 2.3 h, respectively) compared to other documented hyporheic systems, and the net sink threshold compares favorably to the lower boundary of the anaerobic threshold determined for this system with the new oxygen Damkohler number. The consistency of the residence time threshold values of NO₃^? cycling in this study, despite environmental variability and disparate morphology, indicates that NO₃^? hot moment dynamics are primarily driven by changes in physical hydrology and associated residence times. Copyright © 2013 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.     

Hydrology and nitrogen balance of a seasonally inundated Danish floodplain wetland

This paper characterizes a seasonally inundated Danish floodplain wetland in a state close to naturalness and includes an analysis of the major controls on the wetland water and nitrogen balances. The main inputs of water are precipitation and percolation during ponding and unsaturated conditions. Lateral saturated subsurface flow is low. The studied floodplain owes its wetland status to the hydraulic properties of its sediments: the low hydraulic conductivity of a silt–clay deposit on top of the floodplain maintains ponded water during winter, and parts of autumn and spring. A capillary fringe extends to the soil surface, and capillary rise from groundwater during summer maintains near‐saturated conditions in the root zone, and allows a permanently very high evapotranspiration rate. The average for the growing season of 1999 is 3·6 mm day^?1 and peak rate is 5·6 mm day^?1. In summer, the evapotranspiration is to a large degree supplied by subsurface storage in a confined peat layer underlying the silt–clay. The floodplain sediments are in a very reduced state as indicated by low sulphate concentrations. All nitrate transported into the wetland is thus denitrified. However, owing to modest water exchange with surrounding groundwater and surface water, denitrification is low; 71 kg NO₃–N ha^?1 during the study period of 1999. Reduction of nitrate diffusing into the sediments during water ponding accounts for 75% of nitrate removal. Biomass production and nitrogen uptake in above‐ground vegetation is high—8·56 t dry matter ha^?1 year^?1 and 103 kg N ha^?1 year^?1. Subsurface ammonium concentrations are high, and convective upward transport into the root zone driven by evapotranspiration amounted to 12·8 kg N ha^?1year^?1. The floodplain wetland sediments have a high nitrogen content, and conditions are very favourable for mineralization. Mineralization thus constitutes 72% of above‐ground plant uptake. The study demonstrates the necessity of identifying controlling factors, and to combine surface flow with vadose and groundwater flow processes in order to fully comprehend the flow and nitrogen dynamics of this type of wetland. Copyright © 2004 John Wiley & Sons, Ltd.     

Identification of groundwater recharge sources and processes in a heterogeneous alluvial aquifer: results from multi‐level monitoring of hydrochemistry and environmental isotopes in a riverside agricultural area in Korea

We evaluated sources and pathways of groundwater recharge for a heterogeneous alluvial aquifer beneath an agricultural field, based on multi‐level monitoring of hydrochemistry and environmental isotopes of a riverside groundwater system at Buyeo, Korea. Two distinct groundwater zones were identified with depth: (1) a shallow oxic groundwater zone, characterized by elevated concentrations of NO₃^? and (2) a deeper (>10–14 m from the ground surface) sub‐oxic groundwater zone with high concentrations of dissolved Fe, silica, and HCO₃^?, but little nitrate. The change of redox zones occurred at a depth where the aquifer sediments change from an upper sandy stratum to a silty stratum with mud caps. The δ¹⁸O and δ²H values of groundwater were also different between the two zones. Hydrochemical and δ¹⁸O? δ²H data of oxic groundwater are similar to those of soil water. This illustrates that recharge of oxic groundwater mainly occurs through direct infiltration of rain and irrigation water in the sandy soil area where vegetable cropping with abundant fertilizer use is predominant. Oxic groundwater is therefore severely contaminated by agrochemical pollutants such as nitrate. In contrast, deeper sub‐oxic groundwater contains only small amounts of dissolved oxygen (DO) and NO₃^?. The ³H contents and elevated silica concentrations in sub‐oxic groundwater indicate a somewhat longer mean residence time of groundwater within this part of the aquifer. Sub‐oxic groundwater was also characterized by higher δ¹⁸O and δ²H values and lower d‐excess values, indicating significant evaporation during recharge. We suggest that recharge of sub‐oxic groundwater occurs in the areas of paddy rice fields where standing irrigation and rain water are affected by strong evaporation, and that reducing conditions develop during subsequent sub‐surface infiltration. This study illustrates the existence of two groundwater bodies with different recharge processes within an alluvial aquifer. Copyright © 2009 John Wiley & Sons, Ltd.     

Estimating the influence of increased nitrate loads from wastewater on phosphorus mobility in river sediments

Research on the sediment‐surface water transition zone in three study site regions, different in hydrological conditions, was conducted to estimate to which extent nitrate in surface water can contribute to riverbed sediment oxidation and thus prevent release of sediment phosphorus to surface water. Consequently, the Du tch Flow Model (DUFLOW) based water quality model “Spreewald” and results from the emission model “ Mo delling N utrient E missions in Ri ver S ystems” (MONERIS) were used to estimate to which extent wastewater treatment plants (WWTPs) could contribute to the NO₃^– concentration in surface waters if they were operated without denitrification. It is demonstrated that an effective phosphorus retention in sediments by means of surface water NO₃^– is possible only under specific conditions, i. e. (i) a sufficient supply of surface water to the sediment by advective fluxes, (ii) a sufficient amount of sediment iron to provide phosphorus binding sites in the case of sediment oxidation, (iii) a redox system not leading to a rapid NO₃^– and FeOOH depletion and to phosphorus release from organic pools by high microbial activities. Model results show that in‐stream denitrification processes counteract a significant increase of NO₃^– surface water concentrations from WWTPs operated without denitrification during summer, when eutrophication risk through phosphorus is highest. The increase of NO₃^– surface water concentrations in winter due to decreased denitrification in the surface water is of minor relevance for phosphorus release from sediments.     

Stable isotopic and geochemical identification of groundwater evolution and recharge sources in the arid Shule River Basin of Northwestern China

Stable isotopic (δD_VSMOW and δ¹⁸O_VSMOW) and geochemical signatures were employed to constrain the geochemical evolution and sources of groundwater recharge in the arid Shule River Basin, Northwestern China, where extensive groundwater extraction occurs for agricultural and domestic supply. Springs in the mountain front of the Qilian Mountains, the Yumen‐Tashi groundwater (YTG), and the Guazhou groundwater (GZG) were Ca‐HCO₃, Ca‐Mg‐HCO₃‐SO₄ and Na‐Mg‐SO₄‐Cl type waters, respectively. Total dissolved solids (TDS) and major ion (Mg²⁺, Na⁺, Ca²⁺, K⁺, SO₄^2?, Cl^? and NO₃^?) concentrations of groundwater gradually increase from the mountain front to the lower reaches of the Guazhou Basin. Geochemical evolution in groundwater was possibly due to a combination of mineral dissolution, mixing processes and evapotranspiration along groundwater flow paths. The isotopic and geochemical variations in melt water, springs, river water, YTG and GZG, together with the end‐member mixing analysis (EMMA) indicate that the springs in the mountain front mainly originate from precipitation, the infiltration of melt water and river in the upper reaches; the lateral groundwater from the mountain front and river water in the middle reaches are probably effective recharge sources for the YTG, while contribution of precipitation to YTG is extremely limited; the GZG is mainly recharged by lateral groundwater flow from the Yumen‐Tashi Basin and irrigation return flow. The general characteristics of groundwater in the Shule River Basin have been initially identified, and the results should facilitate integrated management of groundwater and surface water resources in the study area. Copyright © 2015 John Wiley & Sons, Ltd.     

Long‐term assessment of nutrient flow pathway dynamics and in‐stream fate in a temperate karst agroecosystem watershed

Nutrient dynamics in karst agroecosystems remain poorly understood, in part due to limited long‐term nested datasets that can discriminate upland and in‐stream processes. We present a 10‐year dataset from a karst watershed in the Inner‐Bluegrass Region of central Kentucky, consisting of nitrate (nitrate‐N [NO₃^?]), dissolved reactive phosphorus (DRP), total organic carbon (TOC), and total ammoniacal‐N (TAN) measurements at nested spring and stream sites as well as flowrate at the watershed outlet. Hydrograph separation techniques were coupled with multiple linear regression and Empirical Mode Decomposition time‐series analysis to determine significance of seasonal processes and to generate continuous estimates of nutrient pathway loadings. Further, we used model results of benthic algae growth and decomposition dynamics from a nearby watershed to assess if transient storage in algal biomass could explain differences in spring and downstream watershed nutrient loading. Results highlight statistically significant seasonality for all nutrients at stream sites, but only for NO₃^? at springs with longitudinal variability showing significant decreases occurring from spring to stream sites for NO₃^? and DRP, and significant increases for TOC and TAN. Pathway loading analysis highlighted the importance of slow flow pathways to source approximately 70% of DRP and 80% of NO₃^?. Results for in‐stream dynamics suggest that benthic autotroph dynamics can explain summer deviations for TOC, TAN, and DRP but not NO₃^?. Regarding upland dynamics, our findings agree well with existing perceptions in karst for N pathways and upland source seasonality but deviate from perceptions that karst conduits are retentive of P, reflecting the limited buffering capacity of the soil profile and conduit sediments in the Inner‐Bluegrass. Regarding in‐stream fate, our findings highlighted the significance of seasonally driven nutrient processing in the bedrock‐controlled streambed to influence nutrient fluxes at the watershed outlet. Contrary to existing perceptions, we found high N attenuation and an unexplained NO₃^? sink in the bedrock stream, leading us to postulate that floating macrophytes facilitate high rates of denitrification.     

Impact of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology and biogeochemistry

Although riparian zones are well known to reduce nitrogen (N) and phosphorus (P) runoff to streams, they also have the potential to affect greenhouse gas (CO₂, N₂O, and CH₄) fluxes to the atmosphere. Following large storms, soil biogeochemical conditions often become more reduced, especially in oxbow depressions and side channels, which can lead to hot moments of greenhouse gas production. Here, we investigate the impact of the remnants of Hurricane Irene and Tropical Storm Lee on riparian zone hydrology (water table: WT), and biogeochemistry (oxidation‐reduction potential [ORP], dissolved oxygen [DO], NO₃^?, PO₄^3?, CO₂, N₂O, CH₄). Results indicate that large storms have the potential to reset WT levels for weeks to months. Overbank flooding at our site following Irene and Lee led to the infiltration of well‐oxygenated water at depth (higher DO and ORP) while promoting the development of anoxic conditions within soil aggregates near the soil surface (increased N₂O and CH₄ fluxes). A short‐term increase in CO₂ emission was observed following Irene at our site where aerobic respiration was water‐limited. Over a 2‐year period, an oxbow depression exhibited higher WT, higher N₂O and CH₄ fluxes (hot moment), higher CO₂ fluxes (seasonal), and lower NO₃^? concentrations (seasonal) than the rest of the riparian zone. However, neither Irene, nor Lee, nor the oxbow depression significantly impacted PO₄^3?. Dissolved organic carbon, ORP, and DO data illustrate the time‐lag (>20 years) between the creation of an oxbow depression and the development of reducing conditions despite clear differences in riparian zone and oxbow WT dynamics.     

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.     

Assessment of the quantitative and qualitative buffer function of an alluvial wetland: hydrological modelling of a large floodplain (Garonne River,France)

For 2 years, water flow‐patterns in the Garonne floodplain of south‐western France were studied in the field and through hydrodynamic modelling (MARTHE Hydrodynamic Software developed by BRGM). Water flow‐paths and the transport of dissolved elements between river and aquifer have been investigated and modelled. In order to quantify the buffer function of the alluvial floodplain, we focused our work on the effect of a major flood on the water flow‐direction, and on nitrate transport. Thus, we showed that the effect of a large flood in the river was rapidly lost with increasing distance from the river. During the observation period, a hydrologically active strip only 300 m wide on either side of the riverbed played a buffering role in absorbing the flood crest. It was also found that meanders favour the exchange between river and alluvial aquifer, shown by the creation of bypasses between the upstream and downstream parts of meanders. This, in turn, contributes to a dilution of nitrates in the phreatic aquifer, which here has higher nitrate content than the surface water; such dilution may result in an overestimation of the denitrification process in the wooded riverbanks. The coupling of chemical measurements—especially of chlorides and nitrate—with modelling of the dissolved‐element transport allows us to establish the water balance for the riparian wetland, and to separate the effect of dilution and denitrification on nitrate concentration. This indicated the existence of areas in the riparian wetlands where denitrification is particularly strong, leading to reductions in nitrate concentrations of 10 to 30 mg/l NO₃^? during the flood. Copyright © 2003 John Wiley & Sons, Ltd.     

Variation in nitrate uptake and denitrification rates across a salinity gradient in Mediterranean semiarid streams

Streams are significant locations for nitrate (NO₃ ^?) processing within landscapes. This is especially important in dry climates given the limited water availability for biological processes elsewhere. In arid and semiarid regions, many streams are naturally saline. Elevated salinity can constrain the structure and function of aquatic organisms, which is expected to increase worldwide being associated to global warming. We investigated whole-reach NO₃ ^? uptake and denitrification in nine semiarid streams of variable water salinity (i.e. from freshwater to hyposaline) to test if NO₃ ^? processing would decrease with increasing salinity. We used pulse additions and Tracer Addition for Spiraling Curve Characterization (TASCC) to measure whole-reach uptake of added NO₃ ^?, and the acetylene block technique to measure sediment denitrification. TASCC results showed that only five of nine streams were able to retain added NO₃ ^?. Of these five retentive streams, four were saline; however, salinity did not control significantly the variation in whole-reach NO₃ ^? uptake observed across streams. Other measured environmental variables such as streambed NH₄ ⁺ and organic carbon availability were better at explaining this variation. Denitrification was detected in all streams except one and its variation across streams was also independent of salinity. Although denitrification rates tended to be high, their contribution to whole-reach NO₃ ^? uptake was insignificant (≤2.16 %). Alternative pathways, heterotrophic assimilation and/or dissimilatory NO₃ ^? reduction to NH₄ ⁺, were probably responsible for most whole-reach NO₃ ^? uptake. Together, our results highlight that the function of streams in controlling external NO₃ ^? inputs is highly variable and salinity does not apparently constrain this role.     

Groundwater cation concentrations in the riparian zone of a forested headwater stream

Groundwater cation concentrations in relation to hydrologic flow paths were studied in the riparian forest zone of a small headwater catchment near Toronto, Ontario. Groundwater entering the riparian zone from uplands showed significant differences in cation concentrations between slope-foot and near-stream locations. Mean Ca, Mg, K, and Na concentrations in shallow groundwater at the upland perimeter of the riparian forest were 65-0, 11-2, 0-7, and 1-8 mg L^?1 respectively. Mean Ca, Mg, K, and Na concentrations in deep groundwater flowing upwards through glacial sands beneath the riparian zone were 52-1, 15-1, 1-3, and 2-6 mg L^?1 respectively. Shallow groundwater emerged as slope-foot springs producing surface rivulets which crossed the riparian zone to the streams. Deep groundwater flowed upward through organic soils into the rivulets and also discharged directly to the streams as bed and bank seepage. Springs had higher Ca concentrations and lower Mg, K, and Na values than rivulets entering the streams. Conversely, Mg, K, and Na concentrations were higher and Ca concentrations were lower in bank seeps in comparison to rivulets. These results suggest that differences in cation concentrations in groundwater entering the streams result from initial contrast in the chemistry of shallow and deep groundwater rather than from the effects of riparian soils and vegetation.