Microtopographical and hydrophysical controls on subsurface flow and solute transport: A continuous solute release experiment in a subarctic bog

Resource extraction and transportation activities in subarctic Canada can result in the unintentional release of contaminants into the surrounding peatlands. In the event of a release, a thorough understanding of solute transport within the saturated zone is necessary to predict plume fate and the potential impacts on peatland ecosystems. To better characterize contaminant transport in these systems, approximately 13,000 L/day of sodium chloride tracer (200 mg/L) was released into a bog in the James Bay Lowland. The tracer was pumped into a fully penetrating well (1.5 m) between July 5 and August 18, 2015. Horizontal and vertical plume development was measured via in situ specific conductance and water table depth from an adaptive monitoring network. Over the spill period, the bulk of the plume travelled a lateral distance of 100 m in the direction of the slight regional groundwater and topographical slope. The plume shape was irregular and followed the hollows, indicating preferential flow paths due to the site microtopography. Saturated transport of the tracer occurred primarily at ~25 cm below ground surface (bgs), and at a discontinuous high hydraulic conductivity layer ~125 cm bgs due to a complex and heterogeneous vertical hydraulic conductivity profile. Plume measurement was confounded by a large amount of precipitation (233 mm over the study period) that temporarily diluted the tracer in the highly conductive upper peat layer. Longitudinal solute advection can be approximated using local water table information (i.e., depth and gradient); microtopography; and meteorological conditions. Vertical distribution of solute within the peat profile is far more complex due to the heterogeneous subsurface; characterization would be aided by a detailed understanding of the site‐specific peat profile; the degree of decomposition; and the type of contaminant (e.g., reactive/nonreactive). The results of this research highlight the difficulty of tracking a contaminant spill in bogs and provide a benchmark for the characterization of the short‐term fate of a plume in these complex systems.     

Towards a conceptual model of hydrological change on an abandoned cutover bog,Quebec

Cutover bogs do not return to functional peatland ecosystems after abandonment because re‐establishment of peat‐forming mosses is poor. This paper presents a conceptual model of bog disturbance caused by peat harvesting (1942–1972), and the hydrological evolution that occurred after abandonment (1973–1998). Two adjacent bogs of similar size and origin, one harvested and the other essentially undisturbed, provide the basis for understanding what changes occurred. The model is based on historical trends evident from previous surveys of land‐use, bog ecology and resource mapping; and from recent hydrological and ecological data that characterize the current condition. Water balance data and historical information suggest that runoff increased and evapotranspiration decreased following drainage, but tended towards pre‐disturbance levels following abandonment, as vegetation recolonized the surface and drainage became less efficient over time. Dewatering of soil pores after drainage caused shrinkage and oxidation of the peat and surface subsidence of approximately 80 cm over 57 years. Comparisons with a nearby natural bog suggest that bulk density in the upper 50 cm of cutover peat increased from 0·07 to 0·13 g cm^?3, specific yield declined from 0·14 to 0·07, water table fluctuations were 67% greater, and mean saturated hydraulic conductivity declined from 4·1 × 10^?5 to 1·3 × 10^?5 cm s^?1. More than 25 years after abandonment, Sphagnum mosses were distributed over broad areas but covered less than 15% of the surface. Areas with ‘good’ Sphagnum regeneration (>10% cover) were strongly correlated with high water tables (mean ?22 cm), especially in zones of seasonal groundwater discharge, artefacts of the extraction history. Forest cover expanded from 5 to 20% of the study area following abandonment. The effect of forest growth (transpiration and interception) and drainage on lowering water levels eventually will be countered by slower water movement through the increasingly dense soil, and by natural ditch deterioration. However, without management intervention, full re‐establishment of natural hydrological functions will take a very long time. Copyright © 2002 John Wiley & Sons, Ltd.     

Sources and sinks of sea salt in a newfoundland blanket bog

Over an oceanic peatland, the concentration of Na in fog averaged 38.1 mgl^?1 compared with 1.8 mgl^?1 in rain, resulting in a significant flux of mineral elements to the surface. Between 16 May and 20 June 1990 the average mass flux of Na to the bog surface by fog, rain, and dry deposition was 21.9, 10.4 and 7.0 mg m^?2 d^?1. There was little long-term storage of Na within the peatland system, where Na losses measured in stream runoff averaged 34.8 mg m² d^?1, and deep groundwater losses 4 mg m^?2 d^?1. Calcium and Mg were preferentially retained in the organic soil, whereas K was relatively mobile. Potassium tended to become concentrated in the unsaturated zone. Stream runoff had a consistently higher pH than groundwater, corresponding to higher Ca and Mg concentrations, which may have been from mineral sources in the headwater ponds. Otherwise, the stream water chemistry was closely related to groundwater in the upper layers of the peat deposit.     

Sap flow and plant water sources for typical vegetation in a subtropical humid karst area of southwest China

Plant water use plays a crucial part in the soil–plant-atmosphere continuum. However, in karst regions, plants frequently suffer from water shortages due to low soil water storage capacity. Therefore, it is necessary to understand plant water consumption (as determined by sap flow) and seasonal variation of water sources to improve water management in karst catchments. In this study, thermal dissipation probes (TDP), calibrated using empirical equations, were used to measure the sap flow of three typical woody vegetations, including Coriaria nepalensis (sparse-shrub), Toona sinensis (secondary forest) and Populus adenopoda (shrub-grass). Oxygen and hydrogen stable isotopes were used to analyze seasonal variation of plant water sources. The results showed that: (1) T. Sinensis (3.89 ± 3.87 L·day⁻¹) had significantly higher daily sap flow than C. nepalensis (0.33 ± 0.37 L·day⁻¹) and P. adenopoda (0.09 ± 0.12 L·day⁻¹); (2) daily sap flow was closely correlated to photosynthetically active radiation (PAR) and vapour pressure deficit (VPD); (3) over the entire study period, plants mainly used water from the surface soil horizons; and (4) a greater proportion of epikarst water was used for C. nepalensis than by T. sinensis and P. adenopoda over the whole growth stage, and more epikarst water was used in early and mid-growth stages compared to the late stage for the three species. This study contributes to a deeper understanding of the plant water use strategies in karst regions, and is helpful for ecosystem management.     

Climatic and topographic limits to the abundance of bog pools

On patterned peatlands, open water pools develop within a matrix of terrestrial vegetation (‘ridges’). Regional patterns in the distribution of ridge–pool complexes suggest that the relative cover of these two surface types is controlled in part by climate wetness, but landscape topography must also be an important controlling factor. In this paper, a functional model that relates relative cover of ridges and pools to climate and surface gradient was developed and tested. The model was formulated in terms of a water budget, based on the differential effects of ridges and pools on losses by evapotranspiration and subsurface flow. It predicts a positive relationship between surface gradient and ridge proportion, with a linear effect related to water supply and ridge hydraulic conductivity, modified at high ridge proportion by differences in evapotranspiration between ridges and pools. The limit to patterned peatland distribution occurs where the surface is completely covered by ridges. The model may be sensitive or insensitive to climate differences between localities, depending on whether hydraulic characteristics of ridge peat co‐vary with water supply. To distinguish between these alternative hypotheses, surface gradient and ridge proportion were surveyed along 20 transects in each of three localities in Scotland that differ threefold in net precipitation to pools. The results of the field survey served to reject the climate‐sensitive hypothesis, but were consistent with the climate‐insensitive hypothesis. Analysis of the residuals suggested that variation within localities was related more to topographic control of water supply than to ridge hydraulic conductivity or developmental stage. Hence, within this maritime climate region, the distribution of ridge–pool complexes and the relative abundance of pools are controlled mainly by topographic variables. Field surveys across both maritime and continental regions are required to confirm a subtle climatic effect that allows pools to occur on higher gradients in drier climates than in wetter climates. Further development and testing of the functional model will provide a stronger basis for assessing potential feedback between climate change, peatland surface structure and methane emission from pools. Copyright © 2006 John Wiley & Sons, Ltd.     

Heuristic numerical and analytical models of the hydrologic controls over vertical solute transport in a domed peat bog,Jura Mountains,Switzerland

We report the results of numerical and analytical simulations to test the hypothesis that downward vertical flow of porewater from the crests of domed alpine and kettle bogs controls vertical porewater distributions of major solutes such as Ca and Mg. The domed Etang de la Gruère bog (EGr), Switzerland, characterized by a vertical downward gradient of 0·04 and stratified layers of peat, is chosen as a field site for the model calibration and evaluation. The middle 4‐m section of the 6·5 m thick bog peat is heavily humified and has a hydraulic conductivity of ～10^?5·6 cm s^?1. Above and below, peat is less humified with a hydraulic conductivity of ～10^?3 cm s^?1. Heuristic finite difference simulations, using Visual MODFLOW, of the bog hydraulics show that the higher conductivity peat at the bog base is critical to create the observed deep, local flow cells that substantively recharge porewater. Model results and Peclet number calculations show that before ～7000 ¹⁴C yr BP diffusion of solutes from underlying mineral soils controlled the vertical distribution of porewater chemistry. From 7000 to ～1250 ¹⁴C BP the porewater chemistry was probably controlled by both upward diffusion and downward advection, and after ～1250 ¹⁴C yr BP porewater chemistry was probably controlled by downward advection. Concentrations of conservative major solutes in the porewaters of alpine, ombrotrophic bogs are the net effect of both downward vertical porewater movement and upward vertical diffusion, the magnitudes of which are delicately poised to the configuration of the bog water table over time and subsurface peat stratigraphy. Copyright © 2002 John Wiley & Sons, Ltd.     

Anisotropy and depth‐related heterogeneity of hydraulic conductivity in a bog peat. II: modelling the effects on groundwater flow

Anisotropy and heterogeneity of hydraulic conductivity (K) are seldom considered in models of mire hydrology. We investigated the effect of anisotropy and heterogeneity on groundwater flow in bog peat using a steady‐state groundwater model. In five model simulations, four sets of K data were used. The first set comprised measured K values from an anisotropic and heterogeneous bog peat. These data were aggregated to produce the following simplified data sets: an isotropic and heterogeneous distribution of K; an isotropic and homogeneous distribution; and an anisotropic and homogeneous distribution. We demonstrate that, where anisotropy and heterogeneity exist, groundwater flow in bog peat is complex. Fine‐scale variations in K have the potential to influence patterns and rates of groundwater flow. However, for our data at least, it is heterogeneity and not anisotropy that has the greater influence on producing complex patterns of groundwater flow. We also demonstrate that patterns and rates of groundwater flow are simplified and reduced when measured K values are aggregated to create a more uniform distribution of K. For example, when measured K values are aggregated to produce isotropy and homogeneity, the rate of modelled seepage is reduced by 28%. We also show that when measured K values are used, the presence of a drainage ditch can increase seepage through a modelled cross‐section. Our work has implications for the accurate interpretation of hydraulic head data obtained from peat soils, and also the understanding of the effect of drainage ditches on patterns and rates of groundwater flow. Copyright © 2002 John Wiley & Sons, Ltd.     

Assessment of flow–ecology relationships for environmental flow standards: a synthesis focused on the southeast USA

ABSTRACT

Environmental flow standards are a management tool that can help to protect the ecosystem services sustained by rivers. Although environmental flow requirements can be assessed using a variety of methods, most of these methods require establishing relationships between flow and habitat of species of concern. Here, we conducted a synthesis of past flow–ecology studies in the southeast USA. For each state or interstate river basin, we used the published data to determine the flow metrics that resulted in the greatest changes in ecological metrics, and the ecological metrics that were most sensitive to hydrologic alteration. The flow metrics that were most important in preserving ecological metrics were high-flow duration and frequency, 3-day maximum and minimum, and number of reversals. The ecological metrics most sensitive to hydrologic alteration were mostly related to presence or absence of key indicator species.     

The role of recharge and evapotranspiration as hydraulic drivers of ion concentrations in shallow groundwater on Everglades tree islands,Florida (USA)

Recently, evapotranspiration has been hypothesized to promote the secondary formation of calcium carbonate year‐round on tree islands in the Everglades by influencing groundwater ions concentrations. However, the role of recharge and evapotranspiration as drivers of shallow groundwater ion accumulation has not been investigated. The goal of this study is to develop a hydrologic model that predicts the chloride concentrations of shallow tree island groundwater and to determine the influence of overlying biomass and underlying geologic material on these concentrations. Groundwater and surface water levels and chloride concentrations were monitored on eight constructed tree islands at the Loxahatchee Impoundment Landscape Assessment (LILA) from 2007 to 2010. The tree islands at LILA were constructed predominately of peat, or of peat and limestone, and were planted with saplings of native tree species in 2006 and 2007. The model predicted low shallow groundwater chloride concentrations when inputs of regional groundwater and evapotranspiration‐to‐recharge rates were elevated, while low evapotranspiration‐to‐recharge rates resulted in a substantial increase of the chloride concentrations of the shallow groundwater. Modeling results indicated that evapotranspiration typically exceeded recharge on the older tree islands and those with a limestone lithology, which resulted in greater inputs of regional groundwater. A sensitivity analysis indicated the shallow groundwater chloride concentrations were most sensitive to alterations in specific yield during the wet season and hydraulic conductivity in the dry season. In conclusion, the inputs of rainfall, underlying hydrologic properties of tree islands sediments and forest structure may explain the variation in ion concentration seen across Everglades tree islands. Copyright © 2012 John Wiley & Sons, Ltd.     

Regionalizing mean annual flow and daily flow variability for basin‐scale sediment and nutrient modelling

River discharges vary strongly through time and space, and quantifying this variability is fundamental to understanding and modelling river processes. The river basin is increasingly being used as the unit for natural resource planning and management; to facilitate this, basin‐scale models of material supply and transport are being developed. For many basin‐scale planning activities, detailed rainfall‐runoff modelling is neither necessary nor tractable, and models that capture spatial patterns of material supply and transport averaged over decades are sufficient. Nevertheless, the data to describe the spatial variability of river discharge across large basins for use in such models are often limited, and hence models to predict river discharge at the basin scale are required. We describe models for predicting mean annual flow and a non‐dimensional measure of daily flow variability for every river reach within a drainage network. The models use sparse river gauging data, modelled grid surfaces of mean annual rainfall and mean annual potential evapotranspiration, and a network accumulation algorithm. We demonstrate the parameterization and application of the models using data for the Murrumbidgee basin, in southeast Australia, and describe the use of these predictions in modelling sediment transport through the river network. The regionalizations described contain less uncertainty, and are more sensitive to observed spatial variations in runoff, than regionalizations based on catchment area and rainfall alone. Copyright © 2006 John Wiley & Sons, Ltd.     

Simulating the water budget of a Prairie Potholes complex from LiDAR and hydrological models in North Dakota,USA

Abstract

Hydrological processes of the wetland complex in the Prairie Pothole Region (PPR) are difficult to model, partly due to a lack of wetland morphology data. We used Light Detection And Ranging (LiDAR) data sets to derive wetland features; we then modelled rainfall, snowfall, snowmelt, runoff, evaporation, the “fill-and-spill” mechanism, shallow groundwater loss, and the effect of wet and dry conditions. For large wetlands with a volume greater than thousands of cubic metres (e.g. about 3000 m³), the modelled water volume agreed fairly well with observations; however, it did not succeed for small wetlands (e.g. volume less than 450 m³). Despite the failure for small wetlands, the modelled water area of the wetland complex coincided well with interpretation of aerial photographs, showing a linear regression with R² of around 0.80 and a mean average error of around 0.55 km². The next step is to improve the water budget modelling for small wetlands.

Editor Z.W. Kundzewicz; Associate editor X. Chen

Citation Huang, S.L., Young, C., Abdul-Aziz, O.I., Dahal, D., Feng, M., and Liu, S.G., 2013. Simulating the water budget of a Prairie Potholes complex from LiDAR and hydrological models in North Dakota, USA. Hydrological Sciences Journal, 58 (7), 1434–1444.     

Optimizing environmental flow and macrophyte management for restoring a large eutrophic lake-marsh system

With increasing environmental degradation from eutrophication, management strategies associated with eutrophic water restoration initiatives are necessary and have garnered wide interest. Macrophytes contribute to water quality improvement in lake-marsh systems through nutrient uptake, while causing considerable water loss through transpiration. In reverse, hydrological variations affect macrophyte growth status and thus phytoremediation performance. The interactions between hydrological and ecological processes in lake-marsh systems are complex, but environmental flow management strategies accounting for these interactions have been rarely proposed. Accordingly, this study combines environmental flow and macrophyte management in the restoration of a large eutrophic lake-marsh system, accounting for interactions between hydrological and nutrient removal processes. We consider both nutrient uptake and transpiration-driven water loss of macrophytes as well as the impacts of hydrological conditions on macrophyte growth status and sediment biological denitrification. Regulating upstream dam operation is an effective measure for environmental flow management. Thus, we develop an optimization model to guide upstream water release while simultaneously regulating macrophyte area in a lake-marsh system, aiming to minimize the ratio of environmental flow demand to reservoir water availability and maintain satisfactory water quality in the system throughout the year. A genetic algorithm is adopted for solving the optimization model. By applying the method in a typical lake-marsh system (Baiyangdian) in China as a case, we introduce a new macrophyte management regime (for area cover and harvesting regimes) and an optimal environmental flow management schedule. Results show that appropriate monthly fluctuations in wetland water level are beneficial to phytoremediation performance, and harvesting macrophytes in stages is effective in reducing transpiration-driven water loss without inordinately damaging nutrient uptake by macrophytes. This study offers a useful tool for lake-marsh system restoration management and highlights the significance of regulating hydrological processes in water quality restoration.     

A low‐dimensional model of bedrock weathering and lateral flow coevolution in hillslopes: 1. Hydraulic theory of reactive transport

This is the first of a two‐part paper exploring the coevolution of bedrock weathering and lateral flow in hillslopes using a simple low‐dimensional model based on hydraulic groundwater theory (also known as Dupuit or Boussinesq theory). Here, we examine the effect of lateral flow on the downward fluxes of water and solutes through perched groundwater at steady state. We derive analytical expressions describing the decline in the downward flux rate with depth. Using these, we obtain analytical expressions for water age in a number of cases. The results show that when the permeability field is homogeneous, the spatial structure of water age depends qualitatively on a single dimensionless number, Hi. This number captures the relative contributions to the lateral hydraulic potential gradient of the relief of the lower‐most impermeable boundary (which may be below the weathering front within permeable or incipiently weathered bedrock) and the water table. A “scaled lateral symmetry” exists when Hi is low: age varies primarily in the vertical dimension, and variations in the horizontal dimension x almost disappear when the vertical dimension z is expressed as a fraction z/H(x) of the laterally flowing system thickness H(x). Taking advantage of this symmetry, we show how the lateral dimension of the advection–diffusion‐reaction equation can be collapsed, yielding a 1‐D vertical equation in which the advective flux downward declines with depth. The equation holds even when the permeability field is not homogeneous, as long as the variations in permeability have the same scaled lateral symmetry structure. This new 1‐D approximation is used in the accompanying paper to extend chemical weathering models derived for 1‐D columns to hillslope domains.     

Application of a spreadsheet hydrological model for computing the long-term water balance of Lake Awassa,Ethiopia

Abstract

The water balance of the closed freshwater Lake Awassa was estimated using a spreadsheet hydrological model based on long-term monthly hydrometeorological data. The model uses monthly evaporation, river discharge and precipitation data as input. The net groundwater flux is obtained from model simulation as a residual of other water balance components. The result revealed that evaporation, precipitation, and runoff constitute 131, 106 and 83 × 10⁶ m³ of the annual water balance of the lake, respectively. The annual net groundwater outflow from the lake to adjacent basins is 58 × 10⁶ m³. The simulated and recorded lake levels fit well for much of the simulation period (1981–1999). However, for recent years, the simulated and recorded levels do not fit well. This may be explained in terms of the combined effects of land-use change and neotectonism, which have affected the long-term average water balance. With detailed long-term hydrogeological and meteorological data, investigation of the subsurface hydrodynamics, and including the effect of land-use change and tectonism on surface water and groundwater fluxes, the water balance model can be used efficiently for water management practice. The result of this study is expected to play a positive role in future sustainable use of water resources in the catchment.     

Hillslope hydrology and wetland response of two small zero‐order boreal catchments on the Precambrian Shield

Two Precambrian Shield zero‐order catchments were monitored from January 2003 to July 2004 to characterize their hydrological and biogeochemical characteristics prior to a forest management experiment. Hydrometric observations were used to examine temporal trends in hillslope‐wetland connectivity and the hillslope runoff processes that control wetland event response. The hillslope groundwater flux from the longer transect (E1) was continuous throughout the study period. Groundwater fluxes from a shorter and steeper hillslope (E0) were intermittent during the study period. Large depression storage elements (termed micro‐basins) located on the upper hillslope of the E1 catchment appeared to be at least partly responsible for the observed rapid wetland runoff responses. These micro‐basins were hydrologically connected to a downslope wetland by a subsurface channel of glacial cobbles that functioned as a macropore channel during episodic runoff events. The runoff response from the hilltop micro‐basins is controlled by antecedent water table position and water is quickly piped to the wetland fringe through the cobble channel during high water table conditions. During periods of low water table position, seepage along the bedrock–soil interface from the hilltop micro‐basin and other hillslopes maintained hillslope–wetland connectivity. The micro‐basins create a dynamic variable source‐area runoff system where the contributing area expands downslope during episodic runoff events. The micro‐basins occupied 30% of the E1 catchment and are a common feature on the Precambrian Shield. Copyright © 2007 John Wiley & Sons, Ltd.     

Effect of bedrock flow on catchment rainfall‐runoff characteristics and the water balance in forested catchments in Tanzawa Mountains,Japan

In this paper, we examined the role of bedrock groundwater discharge and recharge on the water balance and runoff characteristics in forested headwater catchments. Using rigorous observations of catchment precipitation, discharge and streamwater chemistry, we quantified net bedrock flow rates and contributions to streamwater runoff and the water balance in three forested catchments (second‐order to third‐order catchments) underlain by uniform bedrock in Japan. We found that annual rainfall in 2010 was 3130 mm. In the same period, annual discharge in the three catchments varied from 1800 to 3900 mm/year. Annual net bedrock flow rates estimated by the chloride mass balance method at each catchment ranged from ?1600 to 700 mm/year. The net bedrock flow rates were substantially different in the second‐order and third‐order catchments. During baseflow, discharge from the three catchments was significantly different; conversely, peak flows during large storm events and direct runoff ratios were not significantly different. These results suggest that differences in baseflow discharge rates, which are affected by bedrock flow and intercatchment groundwater transfer, result in the differences in water balance among the catchments. This study also suggests that in these second‐order to third‐order catchments, the drainage area during baseflow varies because of differences between the bedrock drainage area and surface drainage area, but that the effective drainage area during storm flow approaches the surface drainage area. Copyright © 2012 John Wiley & Sons, Ltd.     

Estimating fog deposition at a Puerto Rican elfin cloud forest site: comparison of the water budget and eddy covariance methods

The deposition of fog to a wind‐exposed 3 m tall Puerto Rican cloud forest at 1010 m elevation was studied using the water budget and eddy covariance methods. Fog deposition was calculated from the water budget as throughfall plus stemflow plus interception loss minus rainfall corrected for wind‐induced loss and effect of slope. The eddy covariance method was used to calculate the turbulent liquid cloud water flux from instantaneous turbulent deviations of the surface‐normal wind component and cloud liquid water content as measured at 4 m above the forest canopy. Fog deposition rates according to the water budget under rain‐free conditions (0·11 ± 0·05 mm h^?1) and rainy conditions (0·24 ± 0·13 mm h^?1) were about three to six times the eddy‐covariance‐based estimate (0·04 ± 0·002 mm h^?1). Under rain‐free conditions, water‐budget‐based fog deposition rates were positively correlated with horizontal fluxes of liquid cloud water (as calculated from wind speed and liquid water content data). Under rainy conditions, the correlation became very poor, presumably because of errors in the corrected rainfall amounts and very high spatial variability in throughfall. It was demonstrated that the turbulent liquid cloud water fluxes as measured at 4 m above the forest could be only ～40% of the fluxes at the canopy level itself due to condensation of moisture in air moving upslope. Other factors, which may have contributed to the discrepancy in results obtained with the two methods, were related to effects of footprint mismatch and methodological problems with rainfall measurements under the prevailing windy conditions. Best estimates of annual fog deposition amounted to ～770 mm year^?1 for the summit cloud forest just below the ridge top (according to the water budget method) and ～785 mm year^?1 for the cloud forest on the lower windward slope (using the eddy‐covariance‐based deposition rate corrected for estimated vertical flux divergence). Copyright © 2006 John Wiley & Sons, Ltd.     

Dynamics of stream nitrate sources and flow pathways during stormflows on urban,forest and agricultural watersheds in central Pennsylvania,USA

Understanding the influence of storm events on nitrate (NO₃^?) dynamics is important for efficiently managing NO₃^? pollution. In this study, five sites representing a downstream progression of forested uplands underlain by resistant sandstone to karst lowlands with agricultural, urban and mixed land‐use were established in Spring Creek, a 201 km² mixed land‐use watershed in central Pennsylvania, USA. At each site, stream water was monitored during six storm events in 2005 to assess changes in stable isotopes of NO₃^? (δ¹⁵N‐NO₃^? and δ¹⁸O‐NO₃^?) and water (δ¹⁸O‐H₂O) from baseflow to peakflow. Peakflow fractions of event NO₃^? and event water were then computed using two‐component mixing models to elucidate NO₃^? flow pathway differences among the five sites. For the forested upland site, storm size appeared to affect NO₃^? sources and flow pathways. During small storms (<35 mm rainfall), greater event NO₃^? fractions than event water fractions indicated the prevalence of atmospheric NO₃^? source contributions at peakflow. During larger storms (>35 mm rainfall), event NO₃^? fractions were less than event water fractions at peakflow suggesting that NO₃^? was flushed from stored sources via shallow subsurface flow pathways. For the urbanized site, wash‐off of atmospheric NO₃^? was an important NO₃^? source at peakflow, especially during short‐duration storms where event water contributions indicated the prevalence of overland flow. In the karst lowlands, very low fractions of event water and even lower fractions of event NO₃^? at peakflow suggested the dominance of ground water flow pathways during storms. These ground water flow pathways likely flushed stored NO₃^? sources into the stream, while deep soils in the karst lowlands also may have promoted NO₃^? assimilation. The results of this study illustrated how NO₃^? isotopes and δ¹⁸O‐H₂O could be combined to show key differences in water and NO₃^? delivery between forested uplands, karst valleys and fully urbanized watersheds. Copyright © 2009 John Wiley & Sons, Ltd.