Influence of sea salt on stream water chemistry in an upland afforested catchment

The chemistry of bulk precipitation and stream water was monitored in an acidic afforested catchment at Llyn Brianne in upland Wales between 1985 and 1990. Throughfall, stemflow and soil water chemistry were also monitored between 1988 and 1989. Marine-derived solutes dominated the ionic composition of precipitation and stream water, which had mean Cl concentrations of 113 μequiv. 1^?1 and 245 μequiv. 1^?1, respectively. The higher concentrations in stream water reflect occult and dry deposition on the forest canopy and the effect of interception and transpiration losses. Chloride variations in stream water (112-454μequiv. 1^?1) were damped compared with bulk precipitation (28-762μequiv. 1^?1) due to the mixing of event (‘new’) water with pre-event (‘old’) water in the catchment soils. A storm episode monitored in the catchment in April 1989 was associated with high sea salt inputs and Cl concentrations in throughfall (1466μequiv. 1^?1) and storm runoff were exceptionally high (392μequiv. 1^?1). The Cl signal in stream water during the episode was consistent with an event (‘new’) water contribution to the storm response. However, a short-term hydrochemical budget estimated that although Cl outputs from the catchment during the event (1.17 kg ha^?1) were equivalent to 8% of inputs in throughfall and stemflow, the storm runoff was equivalent to 32% of effective precipitation. This indicates that pre-event (‘old’) water was the dominant source (> 75%) of storm runoff. Although sea salt inputs during the event had a marked impact on stream water chemistry, the anomalously high levels of acidity sometimes associated with sea salt events were not observed in this particular study.     

Travel time controls the magnitude of nitrate discharge in groundwater bypassing the riparian zone to a stream on Virginia's coastal plain

Groundwater that bypasses the riparian zone by travelling along deep flow paths may deliver high concentrations of fertilizer‐derived NO₃^? to streams, or it may be impacted by the NO₃^? removal process of denitrification in streambed sediments. In a study of a small agricultural catchment on the Atlantic coastal plain of Virginia's eastern shore, we used seepage meters deployed in the streambed to measure specific discharge of groundwater and its solute concentrations for various locations and dates. We used values of Cl^? concentration to discriminate between bypass water recharged distal to the stream and that contained high NO₃^? but low Cl^? concentrations and riparian‐influenced water recharged proximal to the stream that contained low NO₃^? and high Cl^? concentrations. The travel time required for bypass water to transit the 30‐cm‐thick, microbially active denitrifying zone in the streambed determined the extent of NO₃^? removal, and hydraulic conductivity determined travel time through the streambed sediments. At all travel times greater than 2 days, NO₃^? removal was virtually complete. Comparison of the timescales for reaction and transport through the streambed sediments in this system confirmed that the predominant control on nitrate flux was travel time rather than denitrification rate coefficients. We conclude that extensive denitrification can occur in groundwater that bypasses the riparian zone, but a residence time in biologically active streambed sediments sufficient to remove a large fraction of the NO₃^? is only achieved in relatively low‐conductivity porous media. Instead of viewing them as separate, the streambed and riparian zone should be considered an integrated NO₃^? removal unit. Copyright © 2011 John Wiley & Sons, Ltd.     

Linking transit times to catchment sensitivity to atmospheric deposition of acidity and nitrogen in mountains of the western United States

Transit times are hypothesized to influence catchment sensitivity to atmospheric deposition of acidity and nitrogen (N) because they help determine the amount of time available for infiltrating precipitation to interact with catchment soil and biota. Transit time metrics, including fraction of young water (F_yw) and mean transit time (MTT), were calculated for 11 headwater catchments in mountains of the western United States based on differences in the amplitude of the seasonal signal of δ¹⁸O in streamflow and precipitation. Results were statistically compared with catchment characteristics to elucidate controlling mechanisms. Transit times also were compared with stream solute concentrations to test the hypothesis that transit times are a primary influence on weathering rates and biological assimilation of atmospherically deposited N. Results indicate that transit times in the study catchments are strongly related to soil, vegetation, and topographic characteristics, with barren terrain (bare rock and talus) and steep slopes linked to high F_yw and short MTT, whereas forest soil (hydrogroup B) was linked to low F_yw and greater MTT. Concentrations of silicate weathering products (Na⁺ and Si) were negatively related to F_yw and barren terrain, and positively related to MTT and forest soil, supporting the concept that weathering fluxes and buffering capacity tend to be low in alpine areas due to short transit times. Nitrate concentrations were positively related to N deposition, catchment slope, and barren terrain, and negatively related to forest, indicating that hydrologic and/or biogeochemical processes associated with steep slopes limit uptake of atmospherically deposited N by biota. Interannual and seasonal variability in transit times and source water contributions in the study catchments was substantial, reflecting the influence of strong temporal variations in snowmelt inputs in high‐elevation catchments of the western United States. Results from this study confirm that short transit times in these areas are a key reason they are highly sensitive to atmospheric pollution and climate change.     

Nutrient budget of a montane evergreen broad‐leaved forest at Ailao Mountain National Nature Reserve,Yunnan, southwest China

Hydrological fluxes and associated nutrient budget were studied during a 2 year period (1998–99) in a montane moist evergreen broad‐leaved forest at Ailao Mountain, Yunnan. Water samples of rainfall, throughfall, and stemflow, and of surface runoff, soil water, and stream flow were collected bimonthly to determine the concentration and fluxes of nutrients. Soil budgets were determined from the difference between precipitation input (including nutrient leaching from canopy) and output via runoff and drainage. The forest was characterized by low canopy interception and surface runoff, and high percolation and stream flow. Concentrations of nutrients were increased in throughfall and stemflow compared with precipitation. Surface runoff and drainage water had higher nutrient concentrations than precipitation and stream water. Total nitrogen and NH₄⁺‐N concentrations were higher in soil water than stream water, whereas K⁺, Ca²⁺, and Mg²⁺ concentrations were lower in the former than the latter. Annual nutrient fluxes decreased with soil depth following the pattern of water flux. Annual losses of most nutrient elements via stream flow were less than the corresponding inputs via throughfall and stemflow, except for calcium, for which solute loss was greater than the inputs via precipitation. Leaching losses of that element may be compensated by weathering. Losses of nitrogen, phosphorus, potassium, magnesium, sodium, and sulphur could be replaced through atmospheric inputs. Copyright © 2002 John Wiley & Sons, Ltd.     

Does canopy wetness matter? Evapotranspiration from a subtropical montane cloud forest in Taiwan

Evapotranspiration (ET) and canopy wetness were measured over a 2‐year intensive field campaign at the Chi‐Lan Mountain cloud forest site in Taiwan. Eddy covariance and sap flow methods were applied to measure ET and tree sap flow of the endemic yellow cypress (Chamaecyparis obtusa var. formosana). ET was 553 mm yr^?1 over the study period with an annual rainfall and fog deposition of 4893 and 288 mm yr^–1, respectively. The duration of canopy wetness exceeded actual fog or rain events (mostly in the afternoon), and the intercepted water was evaporated later in the following dry morning. The cumulative wet duration accounted for 52% of time over the study period, which was longer than the duration of rainfall and fog altogether (41%). As it adapted to the extremely moist environment, the yellow cypress behaved in a wet‐enhanced/dry‐reduced water use strategy and was sensitive to short periods of dry atmosphere with high evaporation potential. During dry days, the sap flow rate rose quickly after dawn and led to conservative water use through midday and the afternoon. During periodically wet days, the canopy was mostly wetted in the morning, and the interception evaporation contributed largely to the morning ET. The initiation of morning sap flow was postponed 1–3 h, and the sap flow rate tended to peak later at midday. The midday canopy conductance was higher in the periodically wet days (10.6 mm s^–1) as compared with 7.6 mm s^?1 in the dry days. Consequently, the dry‐reduced water use strategy led to much lower annual ET with respect to the available energy (~46%) and high precipitation input (~11%). The moist‐adapted ecohydrology we report reveals the vulnerability of montane cloud forests to prolonged fog‐free periods. More research is urgently needed to better understand the resilience of these ecosystems and formulate adaptive management plans. Copyright © 2012 John Wiley & Sons, Ltd.     

Trace element and major ion concentrations and dynamics in glacier snow and melt: Eliot Glacier,Oregon Cascades

We present concentrations of environmentally available (unfiltered acidified 2% v/v HNO₃) As, Cu, Cd, Pb, V, Sr, and major ions including Ca²⁺, Cl^?, and SO₄^2? in a July 2005 and a March 2006 shallow snow profile from the lower Eliot Glacier, Mount Hood, Oregon, and its proglacial stream, Eliot Creek. Low enrichment factors (EF) with respect to crustal averages suggests that in fresh March 2006 snow environmentally available elements are derived primarily from lithogenic sources. Soluble salts occurred in lower and less variable concentrations in July 2005 snow than March 2006. Conversely, environmentally available trace elements occurred in greater and more variable concentrations in July 2005 than March 2006 snow. Unlike major solutes, particulate‐associated trace elements are not readily eluted during the melt season. Additionally, elevated surface concentrations suggest that they are likely added throughout the year via dry deposition. In a 1‐h stream sampling, ratios of dissolved (<0·45 µm) V:Cl^?, Sr:Cl^?, and Cu:Cl^? are enriched in the Eliot Stream with respect to their environmentally available trace element to Cl^? ratios in Eliot Glacier snow, suggesting chemical weathering additions in the stream waters. Dissolved Pb:Cl^? is depleted in the Eliot Stream with respect to the ratio of environmentally available Pb to Cl^? in snow, corresponding to greater adsorption onto particles at greater pH values. Copyright © 2009 John Wiley & Sons, Ltd.     

Factors controlling the acid‐neutralizing capacity of Japanese cedar forest watersheds in stands of various ages and topographic characteristics

Acid‐neutralizing capacity (ANC) is an important index for streamwater acidification caused by external factors (i.e. chronic acid deposition) and internal factors such as soil acidification due to nitrification. In this study, the influence of forest clear‐cutting and subsequent regrowth on internal acidification was investigated in central Japan, where stream pH (near 7·0) and ANC (above 0·1 meq L^?1) are high. pH, the concentrations of major cations (Na⁺, K⁺, Mg²⁺ and Ca²⁺), major anions (NO₃^?, Cl^? and SO₄^2?) and dissolved silica (Si), and ANC were measured in 33 watersheds of various stand ages, during 2002 to 2004. Only NO₃^? concentration decreased with stand age, whereas pH, ANC, and concentrations of the sum of base cations (BC) and Si were negatively correlated with the minimum elevation of the watershed. The correlation between the BC/Si ratio and minimum elevation suggested that factors contributing to acid neutralization changed at 1100 m above sea level. In watersheds at lower elevations (?1100 m), the relatively high contribution of soil water with longer soil contact times should result in higher ANC, and cation exchange reactions should be the dominant process for acid neutralization due to deposition of colluvial soils on the lower slope. In contrast, in higher‐elevation watersheds (≥1100 m), weathered residual soils are thin and the small contribution of deeper groundwater results in lower ANC. These results suggest that the local acid sensitivity is determined by the hydrological and geomorphologic factors generated by steep topography. Copyright © 2008 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.     

Assessing the role of forests in mitigating eutrophication downstream of pasture during spring snowmelt

Little research has examined whether forests reduce stream water eutrophication in agricultural areas during spring snowmelt periods. This study evaluated the role of forests in ameliorating deteriorated stream water quality in agricultural areas, including pasture, during snowmelt periods. Temporal variation in stream water quality at a mixed land‐use basin (565 ha: pasture 13%, forestry 87%), northern Japan, was monitored for 7 years. Synoptic stream water sampling was also conducted at 16 sites across a wide range of forest and agricultural areas in a basin (18.3 km²) in spring, summer and fall. Atmospheric nitrogen (N) and phosphorus (P) deposition were measured for 4 years. The results showed that concentration pulses of nitrate, organic N and total P in stream water were observed when discharge increased during spring snowmelt. Their concentrations were high when silicate concentrations were low, suggesting surface water exported from pasture largely contributed to stream water pollution during snowmelt. Atmospheric N and P deposition (4.1 kg N ha^?1 y^?1; 0.09 kg P ha^?1 y^?1, respectively) was too low to affect the background concentrations of N and P in streams from forested areas. Reduction of eutrophication caused by nutrients from pasture was mainly due to dilution by water containing low concentrations of N and P exported from forested areas, whereas in‐stream reduction was not a dominant process. Results indicate that forests have a limited capacity to reduce the concentration pulses of N and P in stream water during snowmelt in this study basin. Copyright © 2014 John Wiley & Sons, Ltd.     

Spatial aggregation of time‐variant stream water ages in urbanizing catchments

We calibrated an integrated flow–tracer model to simulate spatially distributed isotope time series in stream water in a 7.9‐km² catchment with an urban area of 13%. The model used flux tracking to estimate the time‐varying age of stream water at the outlet and both urbanized (1.7 km²) and non‐urban (4.5 km²) sub‐catchments over a 2.5‐year period. This included extended wet and dry spells where precipitation equated to >10‐year return periods. Modelling indicated that stream water draining the most urbanized tributary was youngest with a mean transit time (MTT) of 171 days compared with 456 days in the non‐urban tributary. For the larger catchment, the MTT was 280 days. Here, the response of urban contributing areas dominated smaller and more moderate runoff events, but rural contributions dominated during the wettest periods, giving a bi‐modal distribution of water ages. Whilst the approach needs refining for sub‐daily time steps, it provides a basis for projecting the effects of urbanization on stream water transit times and their spatial aggregation. This offers a novel approach for understanding the cumulative impacts of urbanization on stream water quantity and quality, which can contribute to more sustainable management. Copyright © 2015 John Wiley & Sons, Ltd.     

Alkalinization and acidification of stream water with changes in atmospheric deposition in a tropical dry evergreen forest of northeastern Thailand

Field surveys on atmospheric deposition and stream water chemistry were conducted in an evergreen forest in northeastern Thailand characterized by a tropical savanna climate with distinct dry and wet seasons. Atmospheric deposition of ion constituents by throughfall and stemflow was shown to increase in the beginning and end of the wet season, reflecting the precipitation pattern. The pH and electrical conductivity of stream water increased with alkalinity and base cation concentrations due to mineralization of organic matter by the first rain and retention of anions in soil during the start of the wet season. After initial alkalinization, the pH and alkalinity declined rapidly with the highest SO₄^2? concentration displayed in the middle towards the end of the wet season. The magnitude of peaks in SO₄^2? concentration (13.5–60.6 μmol_c/L) reflects deposition during the first 2 months of the wet season (March and April) in respective years (60.8–170 mol_c/ha). Release of SO₄^2? with H⁺, which is retained in soil during the early wet season, may cause acidification later in the season. The deposition and concentration of SO₄^2? declined over 6 years. However, the pH of stream water declined with increasing concentrations of SO₄^2? and other major ions. The release of materials accumulated in the ecosystem was facilitated by the decrease in SO₄^2? concentration/deposition and increased precipitation in the middle–late wet season. The retention‐release cycle of SO₄^2? largely contributed to both seasonal and interannual variations in stream water chemistry in the tropical savanna climate studied.     

Hydrogeochemical balance of forest umbrisol profiles (‘Sierra de Gata’, central western Spain)

Three techniques for obtaining soil water solutions (gravitational and matrical waters extracted using both in situ tension lysimeters and in vitro pressure chambers) and their later chemical analysis were performed in order to know the evolution of the soil‐solution composition when water moves down through the soil, from the Ah soil horizon to the BwC‐ or C‐horizons of forest soils located in western Spain. Additionally, ion concentrations and water volumes of input waters to soil (canopy washout) and exported waters (drainage solutions from C‐horizons) were determined to establish the net balance of solutes in order to determine the rates of leaching or retention of ions. A generalized process of sorption or retention of most components (even Cl^?) was observed, from the soil surface to the C‐horizon, in both gravitational and matrical waters, with H₄SiO₄, Mn²⁺, Na⁺, and SO₄^2? being the net exported components from the soil through the groundwater. These results enhance the role of the recycling effect in these forest soils. The net percentages of elements retained in these forest soils, considering the inputs and the outputs balance, were 68% K⁺, 85% Ca²⁺, 58% Mg²⁺, 7% Al³⁺, 5% Fe³⁺, 34% Zn²⁺, 57% Cl^?, and 20% NO₃^?, and about 75% of dissolved organic carbon was mineralized. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of commercial timber harvesting on streamflow regimes in the Plynlimon catchments,mid‐Wales

This paper presents the first large‐scale British study of the impacts of commercial forest cutting on stream‐flow regimes. The 70% forested headwaters of the River Severn are part of the intensively instrumented long‐term Plynlimon catchment study into the impact of land use on stream flow. The forest area, comprising predominantly Sitka spruce (Picea sitchensis), was planted mainly in the 1930s and 1940s. Harvesting commenced in the mid‐1980s and over the study period about half the forest has been felled. Changes in annual water yield and extreme flows were studied in four nested catchments ranging in area from about 1 to 10 km² and compared with an adjacent benchmark grassland catchment. As expected from earlier process studies the cutting of the forest increased total annual flows. Less expected was the clear evidence that the felling augmented low flows. This informs a long‐standing debate whether upland forestry increases or reduces baseflows. A particularly notable result was the lack of impact of the harvesting on storm peak flows. This may result from the application of forest management guidelines designed to reduce soil damage and erosion during the harvesting, and indicates that the forest itself has a limited impact on flooding. These findings are timely because British forest expansion peaked in the 30 years following the Second World War, and large areas of these woodlands are now approaching economic maturity and will be harvested in the next two decades. Copyright © 2004 John Wiley & Sons, Ltd.     

Hydrological flowpaths and nitrate removal rates within a riparian floodplain along a fourth‐order stream in Brittany (France)

Three main reservoirs were identified that contribute to the shallow subsurface flow regime of a valley drained by a fourth‐order stream in Brittany (western France). (i) An upland flow that supplied a wetland area, mainly during the high‐water period. It has high N‐NO₃^? and average Cl^? concentrations. (ii) A deep confined aquifer characterized by low nitrate and low chloride concentrations that supplied the floodplain via flow upwelling. (iii) An unconfined aquifer under the riparian zone with high Cl^? and low N‐NO₃^? concentrations where biological processes removed groundwater nitrate. This aquifer collected the upland flow and supplied a relict channel that controlled drainage from the whole riparian zone. Patterns of N‐NO₃^? and Cl^? concentrations along riparian transects, together with calculated high nitrate removal, indicate that removal occurred mainly at the hillslope–riparian zone interface (i.e. first few metres of wetland), whereas dilution occurred in lower parts of the transects, especially during low‐water periods and at the beginning of recharge periods. Stream flow was modelled as a mixture of water from the three reservoirs. An estimation of these contributions revealed that the deep aquifer contribution to stream flow averaged 37% throughout the study period, while the contribution of the unconfined reservoir below the riparian zone and hillslope flow was more variable (from ca 6 to 85%) relative to rainfall events and the level of the riparian water table. At the entire riparian zone scale, NO₃^? removal (probably from denitrification) appeared most effective in winter, despite higher estimated upland NO₃^? fluxes entering the riparian zone during this period. Copyright © 2003 John Wiley & Sons, Ltd.     

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

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

Rainfall intensity affects runoff responses in a semi-arid catchment

The source and hydrochemical makeup of a stream reflects the connectivity between rainfall, groundwater, the stream, and is reflected to water quantity and quality of the catchment. However, in a semi-arid, thick, loess covered catchment, temporal variation of stream source and event associated behaviours are lesser known. Thus, the isotopic and chemical hydrographs in a widely distributed, deep loess, semi-arid catchment of the northern Chinese Loess Plateau were characterized to determine the source and hydrochemical behaviours of the stream during intra-rainfall events. Rainfall and streamflow were sampled during six hydrologic events coupled with measurements of stream baseflow and groundwater. The deuterium isotope (²H), major ions (Cl⁻, SO₄²⁻, NO₃⁻, Ca²⁺, K⁺, Mg²⁺, and Na⁺) were evaluated in water samples obtained during rainfall events. Temporal variation of ²H and Cl⁻ measured in the groundwater and stream baseflow prior to rainfall was similar; however, the isotope compositions of the streamflow fluctuated significantly and responded quickly to rainfall events, likely due to an infiltration excess, overland dominated surface runoff during torrential rainfall events. Time source separation using ²H demonstrated greater than 72% on average, the stream composition was event water during torrential rainfall events, with the proportion increasing with rainfall intensity. Solutes concentrations in the stream had loglinear relationships with stream discharge, with an outling anomaly with an example of an intra-rainfall event on Oct. 24, 2015. Stream Cl⁻ behaved nonconservative during rainfall events, temporal variation of Cl⁻ indicated a flush and washout at the onset of small rainfall events, a dilution but still high concentration pattern in high discharge and old water dominated in regression flow period. This study indicates rainfall intensity affects runoff responses in a semi-arid catchment, and the stored water in the thick, loess covered areas was less connected with stream runoff. Solute transport may threaten water quality in the area, requiring further analysis of the performance of the eco-restoration project.     

Behaviour of chemical solutes during a storm in a rainforested headwater catchment

The aim of this study is to identify, in a small catchment area located within a tropical forest, the pedological compartments in which the export of nutrients and chemical erosion of solutes occur during a stormflow event. The catchment area displays two types of lateral flow: (i) overland flow at the surface of the soil in the litter and root mat and (ii) groundwater flow in a macroporous subsurface horizon. We interpret the variations of stream‐water chemistry during a storm‐flow event using the separation of storm‐flow hydrograph data between overland and groundwater flow, and (Cl^?) as a chemical parameter characterizing the residence time of water in the soil. It appears that K⁺ especially was released into the throughfall, whereas Ca⁺⁺, Mg⁺⁺ and Na⁺ were clearly released from the litter. K⁺ disappeared rapidly from soil solution, whereas Ca⁺⁺ and Mg⁺⁺ were more progressively absorbed by the vegetation. The Ca⁺⁺ and Mg⁺⁺ contents in groundwater increased with increasing residence time owing to the transpiration of trees. The export of H₄SiO₄ in the overland flow was moderate, i.e. 24% of total H₄SiO₄ export in the stream flow, as overland flow represented 39% of total runoff. The subsurface horizon—where active groundwater flow occurs—was successively affected by chemical erosion during the storm‐flow peak, and then by neoformation of kaolinite favoured by increasing water residence time. Copyright © 2003 John Wiley & Sons, Ltd.     

Spatio‐temporal variability of the isotopic input signal in a partly forested catchment: Implications for hydrograph separation

The isotopic composition of precipitation (D and ¹⁸O) has been widely used as an input signal in water tracer studies. Whereas much recent effort has been put into developing methodologies to improve our understanding and modelling of hydrological processes (e.g., transit‐time distributions or young water fractions), less attention has been paid to the spatio‐temporal variability of the isotopic composition of precipitation, used as input signal in these studies. Here, we investigated the uncertainty in isotope‐based hydrograph separation due to the spatio‐temporal variability of the isotopic composition of precipitation. The study was carried out in a Mediterranean headwater catchment (0.56 km²). Rainfall and throughfall samples were collected at three locations across this relatively small catchment, and stream water samples were collected at the outlet. Results showed that throughout an event, the spatial variability of the input signal had a higher impact on hydrograph separation results than its temporal variability. However, differences in isotope‐based hydrograph separation determined preevent water due to the spatio‐temporal variability were different between events and ranged between 1 and 14%. Based on catchment‐scale isoscapes, the most representative sampling location could also be identified. This study confirms that even in small headwater catchments, spatio‐temporal variability can be significant. Therefore, it is important to characterize this variability and identify the best sampling strategy to reduce the uncertainty in our understanding of catchment hydrological processes.     

Fluxes of inorganic carbon from two forested catchments in the Appalachian mountains

This study uses long‐term records of stream chemistry, discharge and air temperature from two neighbouring forested catchments in the southern Appalachians in order to calculate production of dissolved CO₂ and dissolved inorganic carbon (DIC). One of the pair of catchments was clear‐felled during the period of the study. The study shows that: (1) areal production rates of both dissolved CO₂ and DIC are similar between the two catchments even during and immediately after the period of clear‐felling; (2) flux of total inorganic carbon (dissolved CO₂+ DIC) rises dramatically in response to a catchment‐wide acidification event; (3) DIC and dissolved CO₂ are dominantly released on the old water portion of the discharge and concentrations peak in the early autumn when flows in the study catchments are at their lowest; (4) total fluvial carbon flux from the clear‐felled catchment is 11·6 t km⁻² year⁻¹ and for the control catchment is 11·4 t km⁻² year⁻¹. The total inorganic carbon flux represents 69% of the total fluvial carbon flux. The method presented in the study provides a useful way of estimating inorganic carbon flux from a catchment without detailed gas monitoring. The time series of dissolved CO₂ at emergence to the stream can also be a proxy for the soil flux of CO₂. Copyright © 2005 John Wiley & Sons, Ltd.     

Dissolved organic matter dynamics during the spring snowmelt at a boreal river valley mire complex in Northwest Russia

Boreal mire landscapes are rich in soil carbon and significantly contribute to the carbon input of aquatic ecosystems. They are composed of different mesoscale ecohydrological subunits, whose individual contributions to the water and carbon export of mire catchments are not well understood. The spring snowmelt period is the major hydrological event in the annual water cycle of the boreal regions and strongly influences the carbon flux between the terrestrial and aquatic systems. The aim of this study was (1) to provide a conceptual understanding of the spatial and temporal dynamics of the surface water chemistry along a swamp forest‐fen‐bog gradient during the snowmelt period, (2) to quantify the exported dissolved organic carbon (DOC) content in the runoff and (3) to identify the ecohydrological landscape unit that contributes most to DOC export during the snowmelt period in a heterogeneous mire complex in Northwest Russia. The highest DOC concentrations were detected in the swamp forest, and the lowest concentrations were observed at the treeless bog by the end of the snowmelt period (swamp forest: 37–43 mg l^?1, bog: 13–17 mg l^?1). During the spring snowmelt period, a significant amount (~1.7 g C m^?2) of DOC was transferred by the ~74 mm of runoff from the catchment into the river. Variability in the thawing periods led to differences in the relative contributions of each ecohydrological zone to the carbon export measured at a stream channel draining the studied part of the mire complex. An increased understanding of the variation in DOC concentrations and contributions from the mesoscale ecohydrological subunits to carbon export can help to predict the potential regional loss of DOC based on land cover type under climate change. Copyright © 2015 John Wiley & Sons, Ltd.