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.     

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

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

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.     

Water source characterization through spatiotemporal patterns of major,minor and trace element stream concentrations in a complex,mesoscale German catchment

The link between spatiotemporal patterns of stream water chemistry and catchment characteristics for the mesoscale Dill catchment (692 km²) in Germany is explored to assess the catchment scale controls on water quality and to characterize water sources. In order to record the spatiotemporal pattern, ‘snapshot sampling’ was applied during low, mean and high flow, including 73 nested sites throughout the catchment. Water samples were analysed for the elements Li, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Mo, Ba, Pb and U using inductively‐coupled‐plasma mass spectrometry, and for electric conductivity and pH. Principle component analysis and hierarchical cluster analysis were used to find typical element associations and to group water samples according to their hydrochemical fingerprints. This revealed regional hydrochemical patterns of water quality which were subsequently related to catchment attributes to draw conclusions about the controls on stream chemistry. It was found that various lithologic signals and anthropogenic point source inputs controlled the base flow hydrochemistry. During increased flows, stream waters were diluted causing additional hydrochemical variability in response to heterogeneous precipitation inputs and differences in aquifer storage capacities. The hydrochemical patterns further displayed in‐stream mixing of waters. This implied, that stream waters could be apportioned to the identified water sources throughout the catchment. The basin‐wide hydrochemical variability has the potential to outrange the tracer signatures typically inferred in studies at the hillslope scale and is able to strongly influence the complexity of the catchment output. Both have to be considered for further catchment scale tracer and modelling work. Despite the likelihood of non‐conservative behaviour, the minor and trace elements enhanced the rather qualitative discrimination of the various groundwater types, as the major cations were strongly masked by point source inputs. Copyright © 2007 John Wiley & Sons, Ltd.     

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

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

Melt water chemistry and its impact on stream water quality

Samples of snowpack leachate were collected over a 60 day period of the spring melt season in 1988 and 1989 at a 10 km² upland catchment in the Cairngorm mountains of Scotland. These were analysed for major ions to assess snowpack chemistry dynamics through the spring and to assess the melt water influence on stream water chemistry. The data clearly show preferential elution of sulphate and nitrate over chloride and hydrogen over the other cations during the early melt of 1988. Following the addition of ions to the snow surface, either as snow or later in the season as rain, the elution sequence is reproduced. Comparison of leachate chemistry with stream chemistry samples taken at the basin outlet indicate that snow pack melt water contributes directly to stream water. The stream water chemistry signal is, however, noisy and the stream concentrations are considerably damped relative to the snowpack leachate. This is thought to be a consequence of differential melting within the catchment as the snowpack at lower altitudes is at a more advanced stage of melt and so holds fewer solutes and mixing with groundwater contributions. Temperature observations at different altitudes within the catchment support this interpretation.     

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.     

Quantifying aggregation and change in runoff source in accordance with catchment area increase in a forested headwater catchment

There has been a great deal of research interest regarding changes in flow path/runoff source with increases in catchment area. However, there have been very few quantitative studies taking subscale variability and convergence of flow path/runoff source into account, especially in relation to headwater catchments. This study was performed to elucidate how the contributions and discharge rates of subsurface water (water in the soil layer) and groundwater (water in fractured bedrock) aggregate and change with catchment area increase, and to elucidate whether the spatial variability of the discharge rate of groundwater determines the spatial variability of stream discharge or groundwater contribution. The study area was a 5‐km² forested headwater catchment in Japan. We measured stream discharge at 113 points and water chemistry at 159 points under base flow conditions. End‐member mixing analysis was used to separate stream water into subsurface water and groundwater. The contributions of both subsurface water and groundwater had large variability below 1 km². The contribution of subsurface water decreased markedly, while that of groundwater increased markedly, with increases in catchment area. The specific discharge of subsurface water showed a large degree of variability and decreased with catchment area below 0.1 km², becoming almost constant above 0.1 km². The specific discharge of groundwater showed large variability below 1 km² and increased with catchment area. These results indicated that the variabilities of stream discharge and groundwater contribution corresponded well with the variability of the discharge rate of groundwater. However, below 0.1 km², it was necessary to consider variations in the discharge rates of both subsurface water and groundwater. Copyright © 2016 John Wiley & Sons, Ltd.     

Estimation of mean residence times of subsurface waters using seasonal variation in deuterium excess in a small headwater catchment in Japan

We measured deuterium excess (d = δD ? 8δ¹⁸O) in throughfall, groundwater, soil water, spring water, and stream water for 3 years in a small headwater catchment (Matsuzawa, 0·68 ha) in the Kiryu Experimental Watershed in Japan. The d value represents a kinetic effect produced when water evaporates. The d value of the throughfall showed a sinusoidal change (amplitude: 6·9‰ relative to Vienna standard mean ocean water (V‐SMOW)) derived from seasonal changes in the source of water vapour. The amplitude of this sinusoidal change was attenuated to 1·3–6·9‰ V‐SMOW in soil water, groundwater, spring water, and stream water. It is thought that these attenuations derive from hydrodynamic transport processes in the subsurface and mixing processes at an outflow point (stream or spring) or a well. The mean residence time (MRT) of water was estimated from d value variations using an exponential‐piston flow model and a dispersion model. MRTs for soil water were 0–5 months and were not necessarily proportional to the depth. This may imply the existence of bypass flow in the soil. Groundwater in the hillslope zone had short residence times, similar to those of the soil water. For groundwater in the saturated zone near the spring outflow point, the MRTs differed between shallow and deeper groundwater; shallow groundwater had a shorter residence time (5–8 months) than deeper groundwater (more than 9 months). The MRT of stream water (8–9 months) was between that of shallow groundwater near the spring and deeper groundwater near the spring. The seasonal variation in the d value of precipitation arises from changes in isotopic water vapour composition associated with seasonal activity of the Asian monsoon mechanism. The d value is probably an effective tracer for estimating the MRT of subsurface water not only in Japan, but also in other East Asian countries influenced by the Asian monsoon. Copyright © 2006 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.     

Sources of dissolved organic carbon during stormflow in a headwater agricultural catchment

Increasing dissolved organic carbon (DOC) concentrations have been reported during the last 15 years in streams from the United Kingdom, Northern Europe and North America. Identifying the sources of DOC and the controls of the delivery to the stream is important to understand the significance of these trends. This relies on the availability of observations of DOC dynamics during storm events, since much of the DOC export from soils to streams occurs during high flows. This study analyses DOC data for eight storm events during winter 2005–2006 in a small agricultural experimental catchment—the Kervidy‐Naizin experimental catchment—located in Western France. A four end‐member mixing approach was applied to the eight monitored storm events to identify DOC sources and quantify their respective contribution to DOC stream fluxes, using DOC, nitrate, sulphate and chloride as tracers. The results show that DOC concentrations in the stream at the outlet of this catchment increase markedly during storm events. The slope of the linear regression between DOC concentration and discharge was not constant for the eight events and depended on pre‐event hydrological conditions. Between 64 and 86% of the DOC that enter the stream during storms originated from the upper layers of the riparian wetland soils. The variation of the delivery of DOC seems to be controlled by hydrological processes only, the wetland soils acting as a non‐limiting store. Copyright © 2009 John Wiley & Sons, Ltd.     

Hydrological flow paths controlling stream chemistry in Japanese forested watersheds

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

Effects of basin size on low-flow stream chemistry and subsurface contact time in the Neversink River watershed,New York

The effects of basin size on low-flow stream chemistry and subsurface contact time were examined for a part of the Neversink River watershed in southern New York State. Acid neutralizing capacity (ANC), the sum of base cation concentrations (SBC), pH and concentrations of total aluminum (Al), dissolved organic carbon (DOC) and silicon (Si) were measured during low stream flow at the outlets of nested basins ranging in size from 0·2 to 166·3 km². ANC, SBC, pH, Al and DOC showed pronounced changes as basin size increased from 0·2 to 3 km², but relatively small variations were observed as basin size increased beyond 3 km². An index of subsurface contact time computed from basin topography and soil hydraulic conductivity also showed pronounced changes as basin size increased from 0·2 to 3 km² and smaller changes as basin size increased beyond 3 km². These results suggest that basin size affects low-flow stream chemistry because of the effects of basin size on subsurface contact time. © 1997 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.     

Defining hydrochemical evolution of streamflow through flowpath dynamics in Kawakami headwater catchment,Central Japan

The hydrochemical behaviour of catchments is often investigated by inferring stream chemistry through identification of source areas involved in hydrograph separation analysis, yet its dynamic evolution of hydrologic pathways has received little attention. Intensive hydrometric and hydrochemical measurements were performed during two different storms on March 29, 2001 and August 21–22, 2001 to define hydrochemical evolution under the dynamic of flow pathways in a 5·2 ha first‐order drainage of the Kawakami experimental basin (KEB), Central Japan, a forested headwater catchment with various soil depths (1·8 to 5 m) overlying late Neogene of volcanic bedrocks. The hydraulic potential distribution and flow lines data showed that the change in flow direction, which was controlled by rainfall amount and antecedent wetness of the soil profile, agreed well with the hydrochemical change across the slope segment during the storm. Hydrograph separation predicted by end‐member mixing analysis (EMMA) using Ca²⁺ and SiO₂ showed that near surface riparian, hillslope soil water and deep riparian groundwater were important in stream flow generation. The evidence of decrease in solutes concentration at a depth of 1 m in the hillslope and 0·6 m in the near surface riparian during peak storm suggested a flushing of high solutes concentration. Most of the solutes accumulated in the deep riparian groundwater zone, which was due to prominent downward flow and agreed well with the residence time. The distinct flow pathways and chemistry between the near surface riparian and deep riparian groundwater zones and the linkage hillslope aquifer and near surface riparian reservoir, which controls rapid flow and solutes flushing during the storm event, are in conflict with the typical assumption that the whole riparian zone resets flow pathways and chemical signature of hillslope soil water, as has been reported in a previous study. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydrological control of dissolved organic carbon dynamics in a forested headwater catchment,Kiryu Experimental Watershed,Japan

To evaluate the influence of hydrological processes on dissolved organic carbon (DOC) dynamics in a forested headwater catchment, DOC concentration was observed along the flow path from rainfall to stream water via throughfall, soil water, groundwater, and spring water for 4 years, and DOC flux through the catchment was calculated. The spatial and temporal variations in DOC concentration and flux were compared with physical hydrological observations and the mean residence time of water. In the upslope soil layer, DOC concentrations were not significantly correlated with water fluxes, suggesting that DOC concentrations were not strictly controlled by water fluxes. In the upslope perennial groundwater, DOC concentration was affected by the change in the amount of microbial degradation of DOC produced by changes in the mean residence time of water. In stream water, the temporal variation in DOC concentration was usually affected by changes in DOC concentration of the inflow component via vertical infiltration from above the perennial groundwater. During dry periods, however, the component from inflow via vertical infiltration was negligible and DOC in the upslope perennial groundwater became the major component of stream water DOC. The temporal variation in stream water DOC concentration during baseflow was affected by rainfall patterns over several preceding months. Therefore, records of rainfall over several preceding months are one of the most important factors for predicting changes in DOC concentration on a catchment scale. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

A model of dissolved organic carbon concentrations in soil and stream waters

The release of dissolved organic carbon (DOC) into drainage waters was modelled using the hydrology of the Birkenes model of stream water chemistry and estimated parameters for the formation and decay of soluble organic matter in the soil. The model was first tested against soil water DOC concentrations over a three year period in the Loch Dee catchment in southwest Scotland. It predicted annual cycles in DOC at one site, but underestimated maximum DOC in the first year, overestimated in the following year, and predicted values very similar to the measured values in the third year. With small modifications to the parameters controlling organic matter addition and decay it successfully predicted DOC variations at two other soil water sites with smaller mean DOC. Further tests were made against short-term DOC variations in a stream draining a subcatchment of Loch Ard in west-central Scotland, using the same decay and addition parameters. Prediction of temporal variation was good, although predicted concentrations were about 25 per cent less than measured values. Considerable potential for the use of fully optimized models of DOC production in soil and stream waters is identified on the basis of these results.     

The role of the hyporheic zone across stream networks

Many hyporheic papers state that the hyporheic zone is a critical component of stream ecosystems, and many of these papers focus on the biogeochemical effects of the hyporheic zone on stream solute loads. However, efforts to show such relationships have proven elusive, prompting several questions: Are the effects of the hyporheic zone on stream ecosystems so highly variable in place and time (or among streams) that a consistent relationship should not be expected? Or, is the hyporheic zone less important in stream ecosystems than is commonly expected? These questions were examined using data from existing groundwater modelling studies of hyporheic exchange flow at five sites in a fifth‐order, mountainous stream network. The size of exchange flows, relative to stream discharge (Q_HEF:Q), was large only in very small streams at low discharge (area ≈ 100 ha; Q < 10 l/s). At higher flows (flow exceedance probability > 0·7) and in all larger streams, Q_HEF:Q was small. These data show that biogeochemical processes in the hyporheic zone of small streams can substantially influence the stream's solute load, but these processes become hydrologically constrained at high discharge or in larger streams and rivers. The hyporheic zone may influence stream ecosystems in many ways, however, not just through biogeochemical processes that alter stream solute loads. For example, the hyporheic zone represents a unique habitat for some organisms, with patterns and amounts of upwelling and downwelling water determining the underlying physiochemical environment of the hyporheic zone. Similarly, hyporheic exchange creates distinct patches of downwelling and upwelling. Upwelling environments are of special interest, because upwelling water has the potential to be thermally or chemically distinct from stream water. Consequently, micro‐environmental patches created by hyporheic exchange flows are likely to be important to biological and ecosystem processes, even if their impact on stream solute loads is small. Published in 2011 by John Wiley & Sons, Ltd.     

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.