Root‐zone moisture replenishment in a native vegetated catchment under Mediterranean climate

The root‐zone moisture replenishment mechanisms are key unknowns required to understand soil hydrological processes and water sources used by plants. Temporal patterns of root‐zone moisture replenishment reflect wetting events that contribute to plant growth and survival and to catchment water yield. In this study, stable oxygen and hydrogen isotopes of twigs and throughfall were continuously monitored to characterize the seasonal variations of the root‐zone moisture replenishment in a native vegetated catchment under Mediterranean climate in South Australia. The two studied hillslopes (the north‐facing slope [NFS] and the south‐facing slope [SFS]) had different environmental conditions with opposite aspects. The twig and throughfall samples were collected every ~20 days over 1 year on both hillslopes. The root‐zone moisture replenishment, defined as percentage of newly replenished root‐zone moisture as a complement to antecedent moisture for plant use, calculated by an isotope balance model, was about zero (±25% for the NFS and ± 15% for the SFS) at the end of the wet season (October), increased to almost 100% (±26% for the NFS and ± 29% for the SFS) after the dry season (April and May), then decreased close to zero (±24% for the NFS and ± 28% for the SFS) in the middle of the following wet season (August). This seasonal pattern of root‐zone moisture replenishment suggests that the very first rainfall events of the wet season were significant for soil moisture replenishment and supported the plants over wet and subsequent dry seasons, and that NFS completed replenishment over a longer time than SFS in the wet season and depleted the root zone moisture quicker in the dry season. The stable oxygen isotope composition of the intraevent samples and twigs further confirms that rain water in the late wet season contributed little to root‐zone moisture. This study highlights the significant role of the very first rain events in the early wet season for ecosystem and provides insights to understanding ecohydrological separation, catchment water yield, and vegetation response to climate changes.     

Spatiotemporal variations of dissolved inorganic carbon and controlling factors in a small karstic catchment,Southwestern China

Dissolved inorganic carbon (DIC) is the most important carbon component in karst aquatic system where fluid is highly transmissive, but has rarely been examined in the subtropical karst critical zone (K-CZ). In this study, concentrations of dissolved solutes and isotopic compositions of DIC (δ¹³C_DIC) at 11 sites of a 73.4 km² karstic catchment in Southwestern China were analysed monthly in order to uncover the spatiotemporal variations of both DIC and its dominant sources, and to identify relevant controlling factors. Both DIC concentrations and δ¹³C_DIC were highly variable, ranging from 2.52 to 5.85 mmol l⁻¹ and from −15.7 to −4.5‰, respectively. DIC in underground water (UGW) was higher in concentration and more depleted in ¹³C compared to surface water (SFS). DIC concentrations showed an inconsistent seasonal trend with other solutes, with higher values in the wet season at some sites. δ¹³C_DIC values were lower in the wet season than in the dry season. The results of mixing model IsoSource revealed spatiotemporal patterns of DIC sources. During the dry season, carbonate weathering was the primary contributor to DIC in UGW (excluding in the middle reaches). However, during the wet season, soil CO₂ was the dominant source of DIC in both UGW and SFS, and it was higher than in the dry season. Overall, there are significant spatiotemporal disparities and highly transmissive characteristics of both DIC and its sources in the K-CZ, which are controlled by multiple factors. This study also highlights that rainfall may play a crucial role in accelerating carbon dynamics in the K-CZ. High-frequency sampling campaigns in high-flow periods and deep analyses are needed in future work to elucidate the related processes and mechanisms. © 2019 John Wiley & Sons, Ltd.     

Water and nitrogen movement through a semiarid dryland agricultural catchment: Seasonal and decadal trends

Water and nutrient budgets in dryland agroecosystems are difficult to manage for efficiency and water quality. This is particularly true where complex terrain and soilscapes interact with pronounced hydrologic seasonality. The purpose of this research was to understand water and hydrologic nitrogen (N) export from a hillslope dryland agroecosystem in a semiarid region where most precipitation occurs outside the growing season. We studied 13 years (2001–2013) of records of water and N inputs and outputs from a 12 ha no‐till artificially drained catchment in the semiarid Palouse Basin of eastern Washington State, USA. Fall‐ and winter‐dominated annual precipitation averaged 462 mm. About 350 mm went to evapotranspiration; crops used ~160 mm from stored soil water during the summer dry‐down season. Soil water replenishment after crop senescence, during the fall wet‐up season, delayed the threshold onset of the high‐discharge season until December. Winter‐dominated drainage fluxes averaged 111 mm or 24% of annual precipitation. Nitrate export in drainage averaged 15 kg·N·ha^?1·year^?1, which was about 10 times the average rate of dissolved organic N export and 15% of the average rate of N application in chemical fertilizer. Fertilizer applications to the catchment were reduced, due to cropping changes, by 1/3 during the last 5 years of the study; however, no corresponding reduction was observed in the nitrate export flux. This lack of change could not be attributed to mineralization of the soil‐organic N legacy of fertilization nor to hydrologic lag of the catchment. Likeliest explanations are (a) despite the reduction, N application continued to exceed crop uptake and accumulation in organic matter; (b) seasonal and interannual variability of catchment connectivity resulted in year‐to‐year field‐scale nitrate storage and carryover. Water and N use efficiencies observed here may be near maximum obtainable for existing crops in this climate. Substantial improvements that would also address multiple environmental issues associated with the N cascade may involve shifts to perennial systems and/or rotations in which N is fixed biologically.     

Seasonal connections between meteoric water and streamflow generation along a mountain headwater stream

In snowmelt-driven mountain watersheds, the hydrologic connectivity between meteoric waters and stream flow generation varies strongly with the season, reflecting variable connection to soil and groundwater storage within the watershed. This variable connectivity regulates how streamflow generation mechanisms transform the seasonal and elevational variation in oxygen and hydrogen isotopic composition (δ¹⁸O and δD) of meteoric precipitation. Thus, water isotopes in stream flow can signal immediate connectivity or more prolonged mixing, especially in high-relief mountainous catchments. We characterized δ¹⁸O and δD values in stream water along an elevational gradient in a mountain headwater catchment in southwestern Montana. Stream water isotopic compositions related most strongly to elevation between February and March, exhibiting higher δ¹⁸O and δD values with decreasing elevation. These elevational isotopic lapse rates likely reflect increased connection between stream flow and proximal snow-derived water sources heavily subject to elevational isotopic effects. These patterns disappeared during summer sampling, when consistently lower δ¹⁸O and δD values of stream water reflected contributions from snowmelt or colder rainfall, despite much higher δ¹⁸O and δD values expected in warmer seasonal rainfall. The consistently low isotopic values and absence of a trend with elevation during summer suggest lower connectivity between summer precipitation and stream flow generation as a consequence of drier soils and greater transpiration. As further evidence of intermittent seasonal connectivity between the stream and adjacent groundwaters, we observed a late-winter flush of nitrate into the stream at higher elevations, consistent with increased connection to accumulating mineralized nitrogen in riparian wetlands. This pattern was distinct from mid-summer patterns of nitrate loading at lower elevations that suggested heightened human recreational activity along the stream corridor. These observations provide insights linking stream flow generation and seasonal water storage in high elevation mountainous watersheds. Greater understanding of the connections between surface water, soil water and groundwater in these environments will help predict how the quality and quantity of mountain runoff will respond to changing climate and allow better informed water management decisions.     

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.     

Seasonal and event-scale variations in solute chemistry for four Sierra Nevada catchments

Hydrobiogeochemical processes controlling stream water chemistry were examined in four small (<5 km²) catchments having contrasting bedrock lithologies in the western Sierra Nevada foothills of California. The Mediterranean climate with its cool/wet and hot/dry cycle produces strong seasonal patterns in hydrological, biological and geochemical processes. Stream water solutes fall into three general groups according to seasonal fluctuation in concentration: strong, rainy season minimum–dry season maximum (Cl⁻, SO₄²⁻, base cations); weak, rainy season minimum–dry season maximum (Si); and rainy season maximum–dry season minimum (NO₃⁻ and K⁺). Solute dynamics in soil solutions and stream water suggest that mixing of drainage waters from bedrock and soil sources regulate stream water solute concentrations. Patterns are further altered by the leaching of solutes accumulated in the soil over the summer period of desiccation and the temporal discoupling of nutrient cycles that occurs due to differences in the timing between vegetation growth (late spring) and leaching (early winter). Solute concentrations are remarkably similar between watersheds with varying bedrock types, with the exception of nitrate, sulfate and bicarbonate. Three watersheds have nitrogen-bearing metasedimentary bedrock that contributes to elevated nitrate concentrations in stream waters. Watersheds whose bedrock includes mineralized veins of sulfide and carbonate minerals similarly have greater sulfate and bicarbonate concentrations in stream water. Hydrobiogeochemical processes are highly dynamic at the seasonal and storm-event temporal scales and spatially complex at the watershed scale making management of stream water chemical composition, such as nitrate concentrations, very challenging.     

The impact of stream-groundwater exchange on seasonal nitrate loads in an urban stream

Urbanization negatively impacts water quality in streams by reducing stream-groundwater interactions, which can reduce a stream's capacity to naturally attenuate nitrate. Meadowbrook Creek, a first order urban stream in Syracuse, New York, has an inverse urbanization gradient, with heavily urbanized headwaters that are disconnected from the floodplain and downstream reaches that have intact riparian floodplains and connection to riparian aquifers. This system allows assessment of how stream-groundwater interactions in urban streams impact the net sources and sinks of nitrate at the reach scale. We used continuous (15-min) streamflow measurements and weekly grab samples at three gauging stations positioned longitudinally along the creek to develop continuous nitrate load estimates at the inlet and outlet of two contrasting reaches. Nitrate load estimates were determined using a USGS linear regression model, RLOADEST, and differences between loads at the inlet and outlet of contrasting reaches were used to quantify nitrate sink and source behaviour year-round. We observed a nitrate load of 1.4 × 10⁴ kg NO₃⁻ per water year, on average, at the outlet of the urbanized reach while the nitrate load at the outlet of the downstream, connected reach was 1.0 × 10⁴ kg NO₃⁻ per water year, on average. We found the more heavily urbanized, hydrologically-disconnected reach was a net source of nitrate regardless of season. In contrast, stream-groundwater exchange caused the hydrologically connected reach to be both a source and sink for nitrate, depending on time of year. Both reaches alter nitrate source and sink behaviour at various spatiotemporal scales. Groundwater connection in the downstream, connected reach reduces annual nitrate loads and provides more opportunities for sources and sinks of nitrate year-round than the hydrologically disconnected stream reach. Mechanisms include groundwater discharge into the stream with variable nitrate concentrations, surface-water groundwater interactions that foster denitrification, and stream load loss to surrounding near-stream aquifers. This study emphasizes how loads are important in understanding how stream-groundwater interactions impact reach scale nitrate export in urban streams.     

Evaluation of nitrate levels in groundwater under agricultural fields in two pilot areas in central Chile: A hydrogeological and geochemical approach

The aim of this study is to evaluate the impact of the application of industrial fertilizers and liquid swine manure in groundwater in two pilot agricultural areas, San Pedro and Pichidegua, which have been under long‐term historic use of fertilizers. A comprehensive hydrogeological investigation was carried out to define the geology and the groundwater flow system. Chemical and isotopic tools were used to evaluate the distribution and behavior of the nitrate in the groundwater. The isotopic tools included δ¹⁸O, δ²H, and ³H, which provide information about the origin and residence time of the groundwater; δ¹⁵N‐NO₃^? and δ¹⁸O‐NO₃^?, which provide information about nitrate sources and processes that can affect nitrate along the groundwater flow system. The application rate of liquid manure and other fertilizers all together with land uses was also evaluated. The hydrogeological investigation identified the presence of a confined aquifer underneath a thick low‐permeability aquitard, whose extension covers most of the two study areas. The nitrate concentration data, excepting a few points in zones located near recharge areas in the upper part of the basins and lower areas at the valley outlets (San Pedro), showed nitrate concentration below 10 mgN/L at the regional scale. The isotope data for nitrate showed no influence of the liquid swine manure in the groundwater at the regional scale, except for the high part of the basins and the outlet of the San Pedro valley, which are areas fertilized by manure. This data showed that the regional aquifer on both pilot study areas is protected by the thick low‐permeability aquitard, which is playing an important role on nitrate attenuation. Evidence of denitrification was also found on both shallow and deep groundwater in the Pichidegua site. This study showed that a comprehensive hydrogeological characterization complemented by chemical and isotope data is key for understanding nitrate distribution and concentration in aquifers from areas with intensive agriculture activities.     

Characteristics of water stable isotopes and hydrograph separation in Baishui catchment during the wet season in Mt.Yulong region,south western China

Glaciers are of crucial importance for the livelihood of the local populations, which depend on their meltwater for water and energy supplies. For this reason, seasonal variations of oxygen‐18 of glacial stream water and their sources within a small glacial catchment in south western China were investigated during the wet season. The results showed significant difference of oxygen‐18 existed among meltwater, rainwater, ground water and stream water, and significantly seasonal variation of precipitation occurred during the observed period. The streamflow of Baishui catchment was separated into components of ice‐snowmelt and precipitation using oxygen‐18. As shown by the result of the two‐component mixing model, on average, 53.4% of the runoff came from ice‐snowmelt during the wet season, whereas the remaining 46.6% were contributed by precipitation in the catchment. According to monthly hydrograph, the contribution of snow and glacier meltwater varied from 40.7% to 62.2%, and that of precipitation varied from 37.8% to 59.3% in wet season. Uncertainties for this separation were mainly caused by the variation of tracer concentrations. The roles of glacier and snow meltwater should be noticed in water resource management in those glacial regions in south western China. Copyright © 2012 John Wiley & Sons, Ltd.     

High spatial-resolution monitoring to investigate nitrate export and its drivers in a mesoscale river catchment along an anthropogenic land-cover gradient

Nitrate monitoring is commonly conducted with low-spatial resolution, only at the outlet or at a small number of selected locations. As a result, the information about spatial variations in nitrate export and its drivers is scarce. In this study, we present results of high-spatial resolution monitoring conducted between 2012 and 2017 in 65 sub-catchments in an Alpine mesoscale river catchment characterized by a land-use gradient. We combined stable isotope techniques with Bayesian mixing models and geostatistical methods to investigate nitrate export and its main drivers, namely, microbial N turnover processes, land use and hydrological conditions. In the investigated sub-catchments, mean values of NO₃⁻ concentrations and its isotope signatures (δ¹⁵N_NO3 and δ¹⁸O_NO3) varied from 2.6 to 26.7 mg L⁻¹, from −1.3‰ to 13.1‰, and from −0.4‰ to 10.1‰, respectively. In this study, land use was an important driver for nitrate export. Very strong and strong positive correlations were found between percentages of agricultural land cover and δ¹⁵N_NO3, and NO₃⁻ concentration, respectively. Mean proportional contributions of NO₃⁻ sources varied spatially and seasonally, and followed land-use patterns. The mean contribution of manure and sewage was much higher in the catchments characterized by a high percentage of agricultural and urban land cover comparing to forested sub-catchments. Specific NO₃⁻ loads were strongly correlated with specific discharge and moderately correlated with NO₃⁻ concentrations. The nitrate isotope and concentration analysis results suggest that nitrate from external sources is stored and accumulated in soil storage pools. Nitrification of reduced nitrogen species in those pools plays the most important role for the N-dynamics in the Erlauf river catchment. Consequently, nitrification of reduced N sources was the main nitrate source except for a number of sub-catchments dominated by agricultural land use. In the Erlauf catchment, denitrification plays only a minor role in controlling NO₃⁻ export on a regional scale.     

Isotope hydrology and water sources in a heavily urbanized stream

Complex networks of both natural and engineered flow paths control the hydrology of streams in major cities through spatio-temporal variations in connection and disconnection of diverse water sources. We used spatially extensive and temporally intensive sampling of water stable isotopes to disentangle the hydrological sources of the heavily urbanized Panke catchment (~220 km²) in the north of Berlin, Germany. The isotopic data enabled us to partition stream water sources across the catchment using a Bayesian mixing analysis. The upper part of the catchment streamflow is dominated by groundwater (~75%) from gravel aquifers. In dry summer periods, streamflow becomes intermittent in the upper catchment, possibly as a result of local groundwater abstractions. Storm drainage dominates the responses to precipitation events. Although such events can dramatically change the isotopic composition of the upper stream network, storm drainage only accounts for 10%–15% of annual streamflow. Moving downstream, subtle changes in sources and isotope signatures occur as catchment characteristics vary and the stream is affected by different tributaries. However, effluents from a wastewater treatment plant (WWTP), serving 700,000 people, dominate stream flow in the lower catchment (~90% of annual runoff) where urbanization effects are more dramatic. The associated increase in sealed surfaces downstream also reduces the relative contribution of groundwater to streamflow. The volume and isotopic composition of storm runoff is again dominated by urban drainage, though in the lower catchment, still only about 10% of annual runoff comes from storm drains. The study shows the potential of stable water isotopes as inexpensive tracers in urban catchments that can provide a more integrated understanding of the complex hydrology of major cities. This offers an important evidence base for guiding the plans to develop and re-develop urban catchments to protect, restore, and enhance their ecological and amenity value.     

A comparison of solute fluxes and sources from glacial and non‐glacial catchments over contrasting melt seasons

Solute and runoff fluxes from two adjacent alpine streams (one glacial and one non‐glacial) were investigated to determine how the inorganic solute chemistry of runoff responded to seasonal and interannual changes in runoff sources and volume, and to differences in physical catchment properties. Intercatchment differences in solute composition were primarily controlled by differences in catchment geology and the presence of soils, whereas differences in total solute fluxes were largely dependent on specific discharge. The glacial stream catchment had higher chemical denudation rates due to the high rates of flushing (higher specific discharge). The non‐glacial Bow River had higher overall concentrations of solutes despite the greater prevalence of more resistant lithologies in this catchment. This is likely the result of both longer average water–rock contact times, and a greater supply of protons from organic soils and/or pyrite oxidation. Increases in snowpack depth/snowmelt runoff reduced the retention of nitrate in the Bow River catchment (i.e. increased nitrate export), probably by reducing net biological uptake, or by reducing the proportion of runoff that had contact with biologically active soil horizons that tend to remove nitrate. The two streams exhibited opposite solute flux responses to climate perturbations over three melt seasons (1998, 1999, and 2000). The 1998 El Niño event resulted in an unusually thin winter snowpack, and increased runoff and solute fluxes from the glacial catchment, but decreased fluxes from the Bow River catchment. Solute fluxes in the Bow River increased proportionally to discharge, indicating that increased snowmelt runoff in this catchment resulted in a proportional increase in weathering rates. In contrast, the proportional variation in solute flux in the glacial stream was only ∼70–80% of the variation in water flux. This suggests that increased ablation of glacier ice and the development of subglacial channels during the 1998 El Niño year apparently reduced the average water–rock contact time in the glacial catchment relative to seasons when the subglacial drainage system was primarily distributed in character. Copyright © 2005 John Wiley & Sons, Ltd.     

Sources and sinks of nutrients in a New Zealand hill pasture catchment III. Nitrogen

A study was made of the nitrogen (N) inputs to, and exports from, a stream draining a pasture catchment near Hamilton, New Zealand, in order to plan measures for minimizing N losses to natural waters. An estimated 7 kg N ha^?1 was exported from the catchment during 1981 of which 86 per cent was in reduced forms (Kjeldahl-N, TKN) and the remainder as nitrate-N (NO₃-N). Virtually all of the reduced N inputs came from saturated overland flow whereas NO₃-N inputs were dominantly subsurface derived. The TKN exported by individual storm events could be predicted (R² = 0.97) from peak flow and from the peak flow rate in the seven days preceding the storm. A TKN balance for eight events showed that except for large floods (return period approximately a year) the stream system was a net sink for TKN. During large floods, scouring of the organic rich seepage areas resulted in the stream system itself being a net source of TKN. Microbial assays for nitrification and denitrification activity indicated that the main nitrate source was the well-aerated greywacke and ash soils and that the permanently saturated seepage zones were a significant nitrate sink. An in-stream nitrate addition experiment showed that up to 20mg N m^?2 h^?1 was removed from the stream. Simultaneous measurements of in situ denitrification activity demonstrated that only about 1 per cent of this removal could be accounted for by denitrification. It was inferred that plant uptake was responsible for the remainder. Retention of near-stream seepage areas is suggested as a measure for minimizing NO₃-N export, whilst removal of stock from seasonally saturated areas during periods of saturatior should reduce soil loss and hence TKN inputs to the stream.     

长江中下游平原升金湖流域硝酸盐来源解析及其不确定性

考虑流域地理特征的空间分异,以升金湖流域人口/农业集约区大渡口(DDK)与森林子流域唐田河(TTH)为研究区,利用贝叶斯同位素混合模型分别解析这2个子流域硝酸盐来源的贡献率,并分析其不确定性. 研究表明:(1)地下水中,DDK?TTH硝酸盐均主要来源于粪便/污水,贡献率可达65%以上,粪便/污水通过土壤下渗导致地下水硝...     

Soil moisture states,lateral flow,and streamflow generation in a semi‐arid,snowmelt‐driven catchment

Hydraulic connectivity on hillslopes and the existence of preferred soil moisture states in a catchment have important controls on runoff generation. In this study we investigate the relationships between soil moisture patterns, lateral hillslope flow, and streamflow generation in a semi‐arid, snowmelt‐driven catchment. We identify five soil moisture conditions that occur during a year and present a conceptual model based on field studies and computer simulations of how streamflow is generated with respect to the soil moisture conditions. The five soil moisture conditions are (1) a summer dry period, (2) a transitional fall wetting period, (3) a winter wet, low‐flux period, (4) a spring wet, high‐flux period, and (5) a transitional late‐spring drying period. Transitions between the periods are driven by changes in the water balance between rain, snow, snowmelt and evapotranspiration. Low rates of water input to the soil during the winter allow dry soil regions to persist at the soil–bedrock interface, which act as barriers to lateral flow. Once the dry‐soil flow barriers are wetted, whole‐slope hydraulic connectivity is established, lateral flow can occur, and upland soils are in direct connection with the near‐stream soil moisture. This whole‐slope connectivity can alter near‐stream hydraulics and modify the delivery of water, pressure, and solutes to the stream. Copyright © 2005 John Wiley & Sons, Ltd.     

Monte Carlo Simulations as a Decision Support to Interpret δ15N Values of Nitrate in Groundwater

Intense farming is often associated with the excessive use of manure or fertilizers and the subsequent deterioration of the groundwater quality in many aquifers worldwide. Stable isotopes of dissolved nitrate (δ¹⁵N and δ¹⁸O) are widely used to determine sources of nitrate contamination and denitrification processes in groundwater but are often difficult to interpret. Thus, Monte Carlo simulations were carried out for a site in lower Bavaria, Germany, in order to explain δ¹⁵N observations in a porous groundwater system with two aquifers, the main aquifer (MA) and several smaller perched aquifers (PA). For evaluating potential contributions, frequency distributions of δ¹⁵N were simulated deriving from (I) the mixing of different nitrate sources, related to land use, as input to groundwater, combined with (II) transport of nitrate in groundwater and (III) microbial denitrification. Simulation results indicate a source-driven isotopic shift to heavier δ¹⁵N values of nitrate in groundwater, which may be explained by land use changes toward a more intensified agriculture releasing high amounts of manure. Microbial denitrification may play a role in the PA, with simulated δ¹⁵N distributions close to the observations. Denitrification processes are however unlikely for the MA, as reasonable simulation curve fits for such a scenario were obtained predominantly for unrealistic portions of nitrate sources and related land use. The applied approach can be used to qualitatively and quantitatively evaluate the influence of different potential contributions, which might mask each other due to overlapping δ¹⁵N ranges, and it can support the estimation of nitrate input related to land use.     

Seasonal and interannual variations of nitrate and chloride in stream waters related to spatial and temporal patterns of groundwater concentrations in agricultural catchments

Nitrate concentrations in streamwater of agricultural catchments often exhibit interannual variations, which are supposed to result from land‐use changes, as well as seasonal variations mainly explained by the effect of hydrological and biogeochemical cycles. In catchments on impervious bedrock, seasonal variations of nitrate concentrations in streamwater are usually characterized by higher nitrate concentrations in winter than in summer. However, intermediate or inverse cycles with higher concentrations in summer are sometimes observed. An experimental study was carried out to assess the mechanisms that determine the seasonal cycles of streamwater nitrate concentrations in intensive agricultural catchments. Temporal and spatial patterns of groundwater concentrations were investigated in two adjacent catchments located in south‐western Brittany (France), characterized by different seasonal variations of streamwater nitrate concentrations. Wells were drilled across the hillslope at depths ranging from 1·5 to 20 m. Dynamics of the water table were monitored and the groundwater nitrate and chloride concentrations were measured weekly over 2 years. Results highlighted that groundwater was partitioned into downslope domains, where denitrification induced lower nitrate concentrations than into mid‐slope and upslope domains. For one catchment, high subsurface flow with high nitrate concentrations during high water periods and active denitrification during low water periods explained the higher streamwater nitrate concentrations in winter than in summer. For the other catchment, the high contribution of groundwater with high nitrate concentrations smoothed or inverted this trend. Increasing bromide/chloride ratio and nitrate concentrations with depth argued for an effect of past agricultural pressure on this catchment. The relative contribution of flows in time and correlatively the spatial origin of waters, function of the depth and the location on the hillslope, and their chemical characteristics control seasonal cycles of streamwater nitrate concentrations and can influence their interannual trends. Copyright © 2004 John Wiley & Sons, Ltd.     

Nitrate removal and young stream water fractions at the catchment scale

Despite extensive research on nitrate export and removal, nutrient contamination remains a major threat to water bodies worldwide. At the local scale, nitrate removal is governed by biogeochemical conditions that vary in space and time, making integration to entire landscapes critical. Water transit times have often been used to describe solute transport, but the relation between water age and nitrate removal at the catchment scale is still poorly understood. We test the hypothesis that nitrate removal peaks when the fraction of young water in discharge is at its minimum, because nitrate removal occurs mostly under dry conditions where deeper, older groundwater dominates streamflow. We tested this hypothesis by exploring a detailed water quality record from the Kervidy–Naizin catchment (FR) and comparing the dynamics of nitrate to those of a conservative solute (chloride). We find that estimates of nitrate removal are consistent with previous estimates at the site and they show a good (inverse) correlation with the fraction of streamflow that is younger than 2.5 months. However, this young water fraction cannot be used to predict nitrate removal in the winter–spring period, when no removal is observed regardless of streamflow age. While this leads us to reject our hypothesis during the winter period, it also suggests that water age distributions and their correlation with nitrate removal can possibly reveal distinct sources of stream water at different hydrologic regimes and relevant biogeochemical reactions.     

Sources of stream sulphate in headwater catchments in Otter Creek Wilderness,West Virginia,USA

Upland forested catchments in the Appalachian Plateau region receive among the greatest rates of atmospheric sulphur (S) deposition in the eastern USA, although coal mines and S‐bearing minerals in bedrock may also contribute to stream acidity in this region. Watershed mass balance and stable S isotopic values (δ³⁴S) of sulphate (SO₄^2?) were used to assess the contributions to stream SO₄^2? from atmospheric and lithogenic sources at Yellow Creek (YC), a headwater catchment on the Appalachian Plateau in West Virginia. Oxygen isotopic values (δ¹⁸O) of water were used to study catchment hydrology. Stream output of SO₄^2? was c. 60% of atmospheric S deposition during a relatively dry year, whereas atmospheric S input was nearly balanced by stream output during a year with above normal amounts of precipitation. The temporal patterns and values of δ³⁴S were similar between bulk precipitation and stream water at two upper elevation sites. At the lowest elevation site, stream δ³⁴S values were similar to bulk precipitation values during the dormant season but were slightly lower than precipitation during the low‐flow summer, probably as the result of a greater proportion of stream water being derived from deep hydrological flowpaths that have contacted S‐bearing minerals with low δ³⁴S values in coal seams. Stream δ³⁴S values at YC were significantly higher than at Coal Run, a catchment containing abandoned coal prospects and having a greater amount of S‐bearing minerals than YC. Results suggested that lithogenic S is a relatively minor source and that atmospheric deposition is the principal source of stream SO₄^2?, and thus stream acidity, at YC. Copyright © 2001 John Wiley & Sons, Ltd.     

A study of the groundwater cycle in Sri Lanka using stable isotopes

The characteristics of the groundwater cycle were researched using stable isotope technology in western Sri Lanka where climatic conditions change greatly within a relatively short distance. The effects of local climate, surface water and topography on the groundwater cycle in the study area with similar geological conditions were investigated. Sri Lanka can be divided spatially into a dry zone, an intermediate zone and a wet zone, and also temporally into the rainy season and the dry season. The zonal characteristics of the groundwater cycle were also elucidated using stable isotopic technology. As an input δ diagram of precipitation in the study area, there are obvious seasonal changes in the isotopic composition and a magnitude effect, both in the wet zone and dry zone. In the wet zone, the slope of the regression line between δ D and δ ¹⁸O and deuterium excess is close to 8 and 10, respectively. However, in the dry zone, the slope of the regression line between δ D and δ ¹⁸O and deuterium excess is much less than 8 and 10, respectively. In the wet zone, there is an obvious seasonal change in the isotopic composition of groundwater. The groundwater was recharged by precipitation during the whole year. The isotopically lighter groundwater was found at the valley bottom in the rainy season there. Under the very heavy precipitation conditions, the slope of the regression line between δ D and δ ¹⁸O and deuterium excess for groundwater was close to 8 and 10, respectively. In other cases, the slopes of the regression lines are less than 8. In the dry zone, the groundwater was recharged by precipitation only in the rainy season. The isotopically lighter groundwater was found on the ridge of the valley in the rainy season. The slope of the regression line between δ D and δ ¹⁸O and deuterium excess for groundwater was much less than 8 and 10, respectively. Copyright © 1999 John Wiley & Sons, Ltd.