Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.     

Groundwater flushing of solutes at wetland and hillslope positions during storm events in a small glaciated catchment in western New York,USA

While the role of groundwater in flushing of solutes has long been recognized, few studies have explicitly studied the within‐event changes in groundwater chemistry. We compared the changes in groundwater chemistry during storm events for a wetland and hillslope position in a small (1·5 ha) glaciated, forested catchment in western New York. Flushing responses for dissolved organic carbon (DOC) and nitrogen (DON), nitrate (NO₃) and sulfate (SO₄) in wetland and hillslope groundwaters were also compared against the corresponding responses in stream water. Eight storm events with varying intensity, amount, and antecedent moisture conditions were evaluated. Solute flushing patterns for wetland and hillslope groundwaters differed dramatically. While DOC concentrations in wetland groundwater followed a dilution trend, corresponding values for hillslope groundwater showed a slight increase. Concentrations for NO₃ in wetland groundwater were below detection limits, but hillslope groundwaters displayed high NO₃ concentrations with a pronounced increase during storm events. Flushing responses at all positions were also influenced by the size of the event and the time between events. We attributed the differences in flushing to the differences in hydrologic flow paths and biogeochemical conditions. Flushing of the wetland did appear to influence storm‐event stream chemistry but the same could not be said for hillslope groundwaters. This suggests that while a variety of flushing responses may be observed in a catchment, only a subset of these responses affect the discharge chemistry at the catchment outlet. Copyright © 2009 John Wiley & Sons, Ltd.     

Insights on stream temperature processes through development of a coupled hydrologic and stream temperature model for forested coastal headwater catchments

Stream temperature controls a number of biological, chemical, and physical processes occurring in aquatic environments. Transient snow cover and advection associated with lateral throughflow inputs can have a dominant influence on stream thermal regimes for headwater catchments in the rain‐on‐snow zone. Most existing stream temperature models lack the ability to properly simulate these processes. We developed and evaluated a conceptual‐parametric catchment‐scale stream temperature model that includes the role of transient snow cover and lateral advection associated with throughflow. The model consists of routines for simulating canopy interception, snow accumulation and melt, hillslope throughflow runoff and temperature, and stream channel energy exchange processes. The model was used to predict discharge and stream temperature for a small forested headwater catchment near Vancouver, Canada, using long‐term (1963–2013) weather data to compute model forcing variables. The model was evaluated against 4 years of observed stream temperature. The model generally predicted daily mean stream temperature accurately (annual RMSE between 0.57 and 1.24 °C) although it overpredicted daily summer stream temperatures by up to 3 °C during extended low streamflow conditions. Model development and testing provided insights on the roles of advection associated with lateral throughflow, channel interception of snow, and surface–subsurface water interactions on stream thermal regimes. This study shows that a relatively simple but process‐based model can provide reasonable stream temperature predictions for forested headwater catchments located in the rain‐on‐snow zone.     

Travel times for snowmelt-dominated headwater catchments: Influences of wetlands and forest harvesting,and linkages to stream water quality

The time it takes water to travel through a catchment, from when it enters as rain and snow to when it leaves as streamflow, may influence stream water quality and catchment sensitivity to environmental change. Most studies that estimate travel times do so for only a few, often rain-dominated, catchments in a region and use relatively short data records (<10 years). A better understanding of how catchment travel times vary across a landscape may help diagnose inter-catchment differences in water quality and response to environmental change. We used comprehensive and long-term observations from the Turkey Lakes Watershed Study in central Ontario to estimate water travel times for 12 snowmelt-dominated headwater catchments, three of which were impacted by forest harvesting. Chloride, a commonly used water tracer, was measured in streams, rain, snowfall and as dry atmospheric deposition over a 31 year period. These data were used with a lumped convolution integral approach to estimate mean water travel times. We explored relationships between travel times and catchment characteristics such as catchment area, slope angle, flowpath length, runoff ratio and wetland coverage, as well as the impact of harvesting. Travel time estimates were then used to compare differences in stream water quality between catchments. Our results show that mean travel times can be variable for small geographic areas and are related to catchment characteristics, in particular flowpath length and wetland cover. In addition, forest harvesting appeared to decrease mean travel times. Estimated mean travel times had complex relationships with water quality patterns. Results suggest that biogeochemical processes, particularly those present in wetlands, may have a greater influence on water quality than catchment travel times.     

Hydrological and catchment controls on event-scale dissolved organic carbon dynamics in boreal headwater streams

Hydrological events transport large proportions of annual or seasonal dissolved organic carbon (DOC) loads from catchments to streams. The timing, magnitude and intensity of these events are very sensitive to changes in temperature and precipitation patterns, particularly across the boreal region where snowpacks are declining and summer droughts are increasing. It is important to understand how landscape characteristics modulate event-scale DOC dynamics in order to scale up predictions from sites across regions, and to understand how climatic changes will influence DOC dynamics across the boreal forest. The goal of this study was to assess variability in DOC concentrations in boreal headwater streams across catchments with varying physiographic characteristics (e.g., size, proportion of wetland) during a range of hydrological events (e.g., spring snowmelt, summer/fall storm events). From 2016 to 2017, continuous discharge and sub-daily chemistry grab samples were collected from three adjacent study catchments located at the International Institute for Sustainable Development-Experimental Lakes Area in northwestern Ontario, Canada. Catchment differences were more apparent in summer and fall events and less apparent during early spring melt events. Hysteresis analysis suggested that DOC sources were proximal to the stream for all events at a catchment dominated by a large wetland near the outlet, but distal from the stream at the catchments that lacked significant wetland coverage during the summer and fall. Wetland coverage also influenced responses of DOC export to antecedent moisture; at the wetland-dominated catchment, there were consistent negative relationships between DOC concentrations and antecedent moisture, while at the catchments without large wetlands, the relationships were positive or not significant. These results emphasize the utility of sub-daily sampling for inferring catchment DOC transport processes, and the importance of considering catchment-specific factors when predicting event-scale DOC behaviour.     

Mobilisation and transport of dissolved organic carbon and iron in peat catchments—Insights from the Lehstenbach stream in Germany using generalised additive models

During the last decades, increasing exports of both dissolved organic carbon (DOC) and iron were observed from peat catchments in North America and Europe with potential consequences for water quality of streamwater and carbon storages of soils. As mobilisation and transport processes of DOC and iron in peat catchments are only partly understood, the purpose of this study was to elucidate these processes in an intensively monitored and studied system. Specifically, it was hypothesised that dissimilatory iron reduction in riparian peatland soils mobilises DOC initially adsorbed to iron minerals. During stormflow conditions, both DOC and iron will be transported into the stream network. Ferrous iron may be reoxidised at redox interfaces on its way to the stream, and subsequently, ferric iron could be transported together with DOC as complexes. To test these hypotheses, generalised additive models (GAMs) were applied to 14 years of weekly time series of discharge and concentrations of selected solutes measured in a German headwater stream called Lehstenbach. This stream drains a 4.19‐km² forested mountain catchment; one third of which is covered by riparian peatland soils. We interpreted results of different types of GAM in the way that (a) iron reduction drove the mobilisation of DOC from peatland soils and that (b) both iron and DOC were transported as complexes after their joint mobilisation to and within the steam. It was speculated that low nitrate availability in the uppermost wetland soil layer, particularly during the growing season, promoted iron reduction and thus the mobilisation of DOC. However, the influence of nitrate on the DOC mobilisation remains relatively uncertain. This influence could be further investigated using methods similar to the GAM analysis conducted here for other catchments with long‐term data as well as detailed measurements of the relevant species in riparian wetland soils and the adjacent stream network.     

Dissolved organic matter variations in coastal plain wetland watersheds: The integrated role of hydrological connectivity,land use,and seasonality

Dissolved organic matter (DOM) is integral to fluvial biogeochemical functions, and wetlands are broadly recognized as substantial sources of aromatic DOM to fluvial networks. Yet how land use change alters biogeochemical connectivity of upland wetlands to streams remains unclear. We studied depressional geographically isolated wetlands on the Delmarva Peninsula (USA) that are seasonally connected to downstream perennial waters via temporary channels. Composition and quantity of DOM from 4 forested, 4 agricultural, and 4 restored wetlands were assessed. Twenty perennial streams with watersheds containing wetlands were also sampled for DOM during times when surface connections were present versus absent. Perennial watersheds had varying amounts of forested wetland (0.4–82%) and agricultural (1–89%) cover. DOM was analysed with ultraviolet–visible spectroscopy, fluorescence spectroscopy, dissolved organic carbon (DOC) concentration, and bioassays. Forested wetlands exported more DOM that was more aromatic‐rich compared with agricultural and restored wetlands. DOM from the latter two could not be distinguished suggesting limited recovery of restored wetlands; DOM from both was more protein‐like than forested wetland DOM. Perennial streams with the highest wetland watershed cover had the highest DOC levels during all seasons; however, in fall and winter when temporary streams connect forested wetlands to perennial channels, perennial DOC concentrations peaked, and composition was linked to forested wetlands. In summer, when temporary stream connections were dry, perennial DOC concentrations were the lowest and protein‐like DOM levels the highest. Overall, DOC levels in perennial streams were linked to total wetland land cover, but the timing of peak fluxes of DOM was driven by wetland connectivity to perennial streams. Bioassays showed that DOM linked to wetlands was less available for microbial use than protein‐like DOM linked to agricultural land use. Together, this evidence indicates that geographically isolated wetlands have a significant impact on downstream water quality and ecosystem function mediated by temporary stream surface connections.     

Flowpath controls on high-spatial-resolution water-chemistry profiles in headwater streams

Stream water chemistry is routinely measured over time at fixed and sparse sites, which provides a coarse image of spatial variability. Here, we measured nitrate, dissolved organic carbon (DOC) and several chemical proxies for water flowpaths, catchment residence time and biogeochemical transformations, every 50–100 m along 13 km of streams in six agricultural headwater catchments (1.1–3.5km²). The objective was to examine controls on longitudinal nitrate profiles at a high spatial resolution during four seasons: rewetting of the catchments in autumn, winter high-flow, spring recession and summer low-flow. Our results showed monotonic trends in longitudinal profiles for nitrate and DOC, which were opposite for the two solutes. Spatial trends in water-chemistry profiles persisted across seasons, which suggests time-invariant controls on the spatial variations in concentrations. Four catchments exhibited decreasing nitrate and increasing DOC from upstream to downstream, while two catchments exhibited increasing nitrate and decreasing DOC. These smooth gradients did not reflect a longitudinal land-use gradient, but rather an increase in the proportion of groundwater inflows when moving downstream, as suggested by the chemical proxies and punctual discharge measurements. Water chemistry also changed abruptly at confluences, at a farm point source and at a localized groundwater inflow zone.     

Spatial variation of wetlands and flux of dissolved organic carbon in boreal headwater streams

In order to investigate the relation between water chemistry and functional landscape elements, spatial data sets of characteristics for 68 small (0·2–1·5 km²) boreal forest catchments in western central Sweden were analysed in a geographical information system (GIS). The geographic data used were extracted from official topographic maps. Water sampled four times at different flow situations was analysed chemically. This paper focuses on one phenomenon that has an important influence on headwater quality in boreal, coniferous forest streams: generation and export of dissolved organic carbon (DOC). It is known that wetland cover (bogs and fens) in the catchment is a major source of DOC. In this study, a comparison was made between a large number of headwater catchments with varying spatial locations and areas of wetlands. How this variation, together with a number of other spatial variables, influences the DOC flux in the streamwater was analysed by statistical methods. There were significant, but not strong, correlations between the total percentages of wetland area and DOC flux measured at a medium flow situation, but not at high flow. Neither were there any significant correlations between the percentage of wetland area connected to streams, nor the percentage of wetland area within a zone 50 m from the stream and the DOC flux. There were, however, correlations between catchment mean slope and the DOC flux in all but one flow situations. This study showed that, considering geographical data retrieved from official sources, the topography of a catchment better explains the variation in DOC flux than the percentage and locations of distinct wetland areas. This emphasizes the need for high‐resolution elevation models accurate enough to reveal the sources of DOC found in headwater streams. Copyright © 2007 John Wiley & Sons, Ltd.     

Significance of processes in the near‐stream zone on stream water acidity in a small acidified forested catchment

The near‐stream zone has received increasing attention owing to its influence on stream water chemistry in general and acidity in particular. Possible processes in this zone include cation exchange, leaching of organic matter and redox reactions of sulphur compounds. In this study the influences of processes in the near‐stream zone on the acidity in runoff from a small, acidified catchment in central southern Sweden were investigated. The study included sampling of groundwater, soil water and stream water along with hydrological measurements. An input–output budget for the catchment was established based on data from the International Co‐operative Programme on Integrated Monitoring at this site. The catchment was heavily acidified by deposition of anthropogenic sulphur, with pH in stream water between 4·4 and 4·6. There was also no relationship between stream flow and pH, which is indicative of chronic acidification. Indications of microbial reduction of sulphate were found in some places near the stream, but the near‐stream zone did not have a general impact on the sulphate concentration in discharging groundwater. The near‐stream zone was a source of dissolved organic carbon (DOC) in the stream, which had a median DOC of 6·8 mg L¹. The influence on stream acidity from organic anions was overshadowed by the effect of sulphate, however, except during a spring flow episode, when additional organic matter was flushed out and the sulphate‐rich ground water was mixed with more diluted event water. Ion exchange was not an important process in the near‐stream zone of the Kindla catchment. Different functions of the near‐stream zone relating to discharge acidity are reported in the literature. In this study there was even a variation within the site. There is therefore a need for more case studies to provide a more detailed understanding of the net effects that the near‐stream zone can have on stream chemistry under different circumstances. Copyright © 2001 John Wiley & Sons, Ltd.     

Effects of bedrock groundwater discharge on spatial variability of dissolved carbon,nitrogen, and phosphorous concentrations in stream water within a forest headwater catchment

The quantitative evaluation of the effects of bedrock groundwater discharge on spatial variability of stream dissolved organic carbon (DOC), dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorous (DIP) concentrations has still been insufficient. We examined the relationships between stream DOC, DIN and DIP concentrations and bedrock groundwater contribution to stream water in forest headwater catchments in warm-humid climate zones. We sampled stream water and bedrock springs at multiple points in September and December 2013 in a 5 km² forest headwater catchment in Japan and sampled groundwater in soil layer in small hillslopes. We assumed that stream water consisted of four end members, groundwater in soil layer and three types of bedrock groundwater, and calculated the contributions of each end member to stream water from mineral-derived solute concentrations. DOC, DIN and DIP concentrations in stream water were compared with the calculated bedrock groundwater contribution. The bedrock groundwater contribution had significant negative linear correlation with stream DOC concentration, no significant correlation with stream DIN concentration, and significant positive linear correlation with stream DIP concentration. These results highlighted the importance of bedrock groundwater discharge in establishing stream DOC and DIP concentrations. In addition, stream DOC and DIP concentrations were higher and lower, respectively, than those expected from end member mixing of groundwater in soil layer and bedrock springs. Spatial heterogeneity of DOC and DIP concentrations in groundwater and/or in-stream DOC production and DIP uptake were the probable reasons for these discrepancies. Our results indicate that the relationships between spatial variability of stream DOC, DIN and DIP concentrations and bedrock groundwater contribution are useful for comparing the processes that affect stream DOC, DIN and DIP concentrations among catchments beyond the spatial heterogeneity of hydrological and biogeochemical processes within a catchment.     

Acidification recovery in a changing climate: Observations from thirty-five years of stream chemistry monitoring in forested headwater catchments at the Turkey Lakes watershed,Ontario

Long-term ecosystem studies are valuable for understanding integrated ecosystem response to global changes in atmospheric deposition and climate. We examined trends for a 35-year period (1982/83–2017/18) in concentrations of a range of solutes in precipitation and stream water from nine headwater catchments spanning elevation and surficial geology gradients at the Turkey Lakes watershed (TLW) in northeastern Ontario, Canada. Average annual water year (WY, October to September) concentrations in precipitation significantly declined over the period for sulphate (SO₄²⁻), nitrate (NO₃⁻) and chloride (Cl⁻), while calcium (Ca²⁺) and potassium (K⁺) concentrations increased, resulting in a significant pH increase from 4.2 to 5.7. Trends in stream chemistry through time are generally consistent with expectations associated with acidification recovery. Concentration of many stream water solutes (SO₄²⁻, Cl⁻, calcium [Ca²⁺], magnesium [Mg²⁺] and NH₄⁺ generally decreased, while others (silica [SiO₂] and dissolved organic carbon [DOC]) generally increased. Increases were also observed for alkalinity (six of nine catchments), acid neutralizing capacity ([ANC]; six of nine catchments) and pH (eight of nine catchments), while conductivity declined (six of nine catchments). Variability in trends among catchments are associated with differences in surficial geology and wetland cover. While absolute solute concentrations were generally lower at bedrock dominated high-elevation catchments compared to till dominated lower elevation catchments, the rate of change of concentration was often greater for high elevation catchments. This study confirms continued, but non-linear stream chemistry recovery from acidification, particularly at the less buffered high and moderate elevation sites. The heterogeneity of responses among catchments highlights our incomplete understanding of the relative importance of different mechanisms influencing stream chemistry and the consequences for downstream ecosystems.     

Seasonal dynamics and exports of elements from a first‐order stream to a large inland lake in Michigan

Headwater streams are critical components of drainage systems, directly connecting terrestrial and downstream aquatic ecosystems. The amount of water in a stream can alter hydrologic connectivity between the stream and surrounding landscape and is ultimately an important driver of what constituents headwater streams transport. There is a shortage of studies that explore concentration–discharge (C‐Q) relationships in headwater systems, especially forested watersheds, where the hydrological and ecological processes that control the processing and export of solutes can be directly investigated. We sought to identify the temporal dynamics and spatial patterns of stream chemistry at three points along a forested headwater stream in Northern Michigan and utilize C‐Q relationships to explore transport dynamics and potential sources of solutes in the stream. Along the stream, surface flow was seasonal in the main stem, and perennial flow was spatially discontinuous for all but the lowest reaches. Spring snowmelt was the dominant hydrological event in the year with peak flows an order of magnitude larger at the mouth and upper reaches than annual mean discharge. All three C‐Q shapes (positive, negative, and flat) were observed at all locations along the stream, with a higher proportion of the analytes showing significant relationships at the mouth than at the mid or upper flumes. At the mouth, positive (flushing) C‐Q shapes were observed for dissolved organic carbon and total suspended solids, whereas negative (dilution) C‐Q shapes were observed for most cations (Na⁺, Mg²⁺, Ca²⁺) and biologically cycled anions (NO₃^?, PO₄^3?, SO₄^2?). Most analytes displayed significant C‐Q relationships at the mouth, indicating that discharge is a significant driving factor controlling stream chemistry. However, the importance of discharge appeared to decrease moving upstream to the headwaters where more localized or temporally dynamic factors may become more important controls on stream solute patterns.     

SULPHATE DYNAMICS IN RELATION TO GROUNDWATER–SURFACE WATER INTERACTIONS IN HEADWATER WETLANDS OF THE SOUTHERN CANADIAN SHIELD

The spatial and temporal distribution of sulphate (SO₄) concentrations in peat pore water and the outlet streams of two forested swamps was related to variations in the magnitude of upland runoff, wetland water levels and flow path. The swamps were located in headwater catchments with contrasting till depths typical of the southern Canadian Shield. Inputs of SO₄ from shallow hillslope tills and streams showed little seasonal variation in either source or concentration in both swamps. Sulphate dynamics at the outlet stream reflected hydrological and biogeochemical processes within the valley wetlands, which in turn were partly controlled by catchment hydrogeology. During high runoff, maximum water table elevations and peak surface flow in the swamps resulted in upland inputs largely bypassing anoxic peat. Consequently, SO₄ concentrations of 8–10 mg/l at the swamp outlets were similar to stream and groundwater inputs. During periods of low flow, concentrations of SO₄ at the swamp outlets declined to less than 3 mg/l. At this time lower water table elevations resulted in increased interaction of input water with anoxic peats, and therefore, SO₄ reduction. Contrasts in till depth and the nature of groundwater flow between catchments resulted in differences in SO₄ dynamics between years and swamps. In dry summers the absence of groundwater inputs to the swamp in the catchment with thin till resulted in a large water table drawdown and re-oxidation of accumulated S, which contributed to maximum SO₄ concentrations (up to 35 mg/l) during storm runoff. Continuous groundwater input to the swamp in the catchment with deeper till was critical to maintaining saturated surfaces and efficient SO₄ retention during both dry and wet summers. A conceptual model of wetland SO₄ retention and export, based on catchment hydrogeology, is developed to generalize the SO₄ dynamics of valley bottom wetlands at the landscape scale. © 1997 by John Wiley & Sons, Ltd.     

Landscape metrics as predictors of hydrologic connectivity between Coastal Plain forested wetlands and streams

Geographically isolated wetlands, those entirely surrounded by uplands, provide numerous landscape‐scale ecological functions, many of which are dependent on the degree to which they are hydrologically connected to nearby waters. There is a growing need for field‐validated, landscape‐scale approaches for classifying wetlands on the basis of their expected degree of hydrologic connectivity with stream networks. This study quantified seasonal variability in surface hydrologic connectivity (SHC) patterns between forested Delmarva bay wetland complexes and perennial/intermittent streams at 23 sites over a full‐water year (2014–2015). Field data were used to develop metrics to predict SHC using hypothesized landscape drivers of connectivity duration and timing. Connection duration was most strongly related to the number and area of wetlands within wetland complexes as well as the channel width of the temporary stream connecting the wetland complex to a perennial/intermittent stream. Timing of SHC onset was related to the topographic wetness index and drainage density within the catchment. Stepwise regression modelling found that landscape metrics could be used to predict SHC duration as a function of wetland complex catchment area, wetland area, wetland number, and soil available water storage (adj‐R² = 0.74, p < .0001). Results may be applicable to assessments of forested depressional wetlands elsewhere in the U.S. Mid‐Atlantic and Southeastern Coastal Plain, where climate, landscapes, and hydrological inputs and losses are expected to be similar to the study area.     

Headwater stream length dynamics across four physiographic provinces of the Appalachian Highlands

Understanding patterns of expansion, contraction, and disconnection of headwater stream length in diverse settings is invaluable for the effective management of water resources as well as for informing research in the hydrology, ecology, and biogeochemistry of temporary streams. More accurate mapping of the stream network and quantitative measures of flow duration in the vast headwater regions facilitate implementation of water quality regulation and other policies to protect waterways. We determined the length and connectivity of the wet stream and geomorphic channel network in 3 forested catchments (<75 ha) in each of 4 physiographic provinces of the Appalachian Highlands: the New England, Appalachian Plateau, Valley and Ridge, and Blue Ridge. We mapped wet stream length 7 times at each catchment to characterize flow conditions between exceedance probabilities of <5% and >90% of the mean daily discharge. Stream network dynamics reflected geologic controls at both regional and local scales. Wet stream length was most variable at two Valley and Ridge catchments on a shale scarp slope and changed the least in the Blue Ridge. The density and source area of flow origins differed between the crystalline and sedimentary physiographic provinces, as the Appalachian Plateau and Valley and Ridge had fewer origins with much larger contributing areas than New England and the Blue Ridge. However, the length and surface connectivity of the wet stream depended on local lithology, geologic structure, and the distribution of surficial deposits such as boulders, glacially derived material, and colluival debris or sediment valley fills. Several proxies indicate the magnitude of stream length dynamics, including bankfull channel width, network connectivity, the base flow index, and the ratio of geomorphic channel to wet stream length. Consideration of geologic characteristics at multiple spatial scales is imperative for future investigations of flow intermittency in headwaters.     

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

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

The relationship between dissolved organic carbon in stream water and soil organic carbon pools at different spatial scales

The relationship between stream water DOC concentrations and soil organic C pools was investigated at a range of spatial scales in subcatchments of the River Dee system in north‐east Scotland. Catchment percentage peat cover and soil C pools, calculated using local, national and international soils databases, were related to mean DOC concentrations in streams draining small‐ (<5 km²), medium‐ (12–38 km²) and large‐scale (56–150 km²) catchments. The results show that, whilst soil C pool is a good predictor of stream water DOC concentration at all three scales, the strongest relationships were found in the small‐scale catchments. In addition, in both the small‐ and large‐scale catchments, percentage peat cover was as a good predictor of stream water DOC concentration as catchment soil C pool. The data also showed that, for a given soil C pool, streams draining lowland (<700 m) catchments had higher DOC concentrations than those draining upland (>700 m) catchments, suggesting that disturbance and land use may have a small effect on DOC concentration. Our results therefore suggest that the relationship between stream water DOC concentration and catchment soil C pools exists at a range of spatial scales and this relationship appears to be sufficiently robust to be used to predict the effects of changes in catchment soil C storage on stream water DOC concentration. Copyright © 1999 John Wiley & Sons, Ltd.     

Linking physiography and evaporation using the isotopic composition of river water in 16 Canadian boreal catchments

Highly seasonal boreal catchments are hydrologically complex and generally data poor and, hence, are ripe for investigation using tracer‐aided hydrologic models. The influence of physiography on isotopic metrics was assessed to identify the catchment characteristics dominating evaporative enrichment. A multiyear stable isotope of water dataset was collected at the outlets of 16 boreal catchments in central Canada ranging in area from 12 to 15,282 km². Physiographic characteristics were obtained through raster analysis of freely available land cover images, stream networks, and digital elevation models. Correlation analysis indicated that as the percentage coverage of open water increased, so too did the evaporative effects observed at the catchment outlet. Correlation to wetland metrics indicated that increasing the percentage coverage of wetlands can reduce or increase evaporative effects observed, depending on the isotopic metric used and the corresponding drainage density, catchment slope, and presence of headwater lakes. The slopes of river evaporative‐mixing lines appear to reflect multifaceted relationships, strongest between catchment slope, headwater lakes, and connected wetlands, whereas mean line‐conditioned excess is more directly linked to physiographic variables. Hence, the slopes of river evaporative‐mixing lines and mean line‐conditioned excess are not interchangeable metrics of evaporative enrichment in a catchment. Relationships identified appear to be independent of catchment scale. These results suggest that adequate inclusion of the distribution of open water throughout a catchment, adequate representation of wetland processes, catchment slope, and drainage density are critical characteristics to include in tracer‐aided hydrologic models in boreal environments in order to minimize structural uncertainty.     

Spatial delineation of groundwater–surface water interactions through intensive in‐stream profiling

The dominance of ‘old’ pre‐event water in headwater storm runoff has been recorded in numerous upland catchment studies; however, the mechanisms by which this pre‐event water enters the stream channel are poorly understood. Understanding these processes is fundamental to determining the controls on surface water quality and associated impacts on stream ecology. Previous studies in the upland forested catchment of the Afon Hafren (River Severn) at Plynlimon, mid‐Wales, identified an active bedrock groundwater system that was discharging into the stream channel during storm response. Detailed analysis showed that these discharges were small and could not account for the majority of pre‐event storm water response identified at this site; pre‐event storm runoff had to be sourced predominantly from further upstream. An intensive stream survey was used to determine the spatial nature of groundwater–surface water (GW–SW) interactions in the Hafren Catchment. Detailed physico‐chemical in‐stream profiling identified a marked change in water quality indicating a significant discrete point of bedrock groundwater discharge upstream of the Hafren Transect study site. The in‐stream profiling showed the importance of high spatial resolution sampling as a key to understanding processes of GW–SW interaction and how quick and cost‐effective measurements of specific electrical conductance of stream waters could be used to highlight in‐stream heterogeneity. This approach is recommended for use in headwater catchments for initial characterisation of the stream channel in order to better locate instrumentation and to determine more effective targeted sampling protocols in upland catchment research. Copyright © 2012 John Wiley & Sons, Ltd.