Transfer of carbon dioxide and methane through the soil‐water‐atmosphere system at Mer Bleue peatland,Canada

Surface waters associated with peatlands, supersaturated with CO₂ and CH₄ with respect to the atmosphere, act as important pathways linking a large and potentially unstable global repository of C to the atmosphere. Understanding the drivers and mechanisms which control C release from peatland systems to the atmosphere will contribute to better management and modelling of terrestrial C pools. We used non‐dispersive infra‐red (NDIR) CO₂ sensors to continuously measure gas concentrations in a beaver pond at Mer Bleue peatland (Canada); measurements were made between July and August 2007. Concentrations of CO₂ in the surface water (10 cm) reached 13 mg C l^?1 (epCO₂ 72), and 26 mg C l^?1 (epCO₂ 133) at depth (60 cm). The study also showed large diurnal fluctuations in dissolved CO₂ which ranged in amplitude from ～1·6 mg C l^?1 at 10 cm to ～0·2 mg C l^?1 at 60 cm depth. CH₄ concentration and supersaturation (epCH₄) measured using headspace analysis averaged 1·47 mg C l^?1 and 3252, respectively; diurnal cycling was also evident in CH₄ concentrations. Mean estimated evasion rates of CO₂ and CH₄ over the summer period were 44·92 ± 7·86 and 0·44 ± 0·25 µg C m^?2s^?1, respectively. Open water at Mer Bleue is a significant summer hotspot for greenhouse gas emissions within the catchment. Our results suggest that CO₂ concentrations during the summer in beaver ponds at Mer Bleue are strongly influenced by biological processes within the water column involving aquatic plants and algae (in situ photosynthesis and respiration). In terms of carbon cycling, soil‐stream connectivity at this time of year is therefore relatively weak. Copyright © 2008 John Wiley & Sons, Ltd.     

Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream

The stable isotopic composition of dissolved inorganic carbon (δ¹³C‐DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed δ¹³C‐DIC increased between 3–5‰ from the stream source to the outlet weir approximately 0·5 km downstream, concomitant with increasing pH and decreasing PCO₂. An increase in δ¹³C‐DIC of 2·4 ± 0·1‰ per log unit decrease of excess PCO₂ (stream PCO₂ normalized to atmospheric PCO₂) was observed from downstream transect data collected during snowmelt. Isotopic fractionation of DIC due to CO₂ outgassing rather than exchange with atmospheric CO₂ may be the primary cause of increased δ¹³C‐DIC values downstream when PCO₂ of surface freshwater exceeds twice the atmospheric CO₂ concentration. Although CO₂ outgassing caused a general increase in stream δ¹³C‐DIC values, points of localized groundwater seepage into the stream were identified by decreases in δ¹³C‐DIC and increases in DIC concentration of the stream water superimposed upon the general downstream trend. In addition, comparison between snowmelt, early spring and summer seasons showed that DIC is flushed from shallow groundwater flowpaths during snowmelt and is replaced by a greater proportion of DIC derived from soil CO₂ during the early spring growing season. Thus, in spite of effects from CO₂ outgassing, δ¹³C of DIC can be a useful indicator of groundwater additions to headwater streams and a tracer of carbon dynamics in catchments. Copyright © 2007 John Wiley & Sons, Ltd.     

Seasonal controls on DOC dynamics in nested upland catchments in NE Scotland

Spatial and temporal variability of hydrological responses affecting surface water dissolved organic carbon (DOC) concentrations are important for determining upscaling patterns of DOC export within larger catchments. Annual and intra‐annual variations in DOC concentrations and fluxes were assessed over 2 years at 12 sites (3·40–1837 km²) within the River Dee basin in NE Scotland. Mean annual DOC fluxes, primarily correlated with catchment soil coverage, ranged from 3·41 to 9·48 g m^?2 yr^?1. Periods of seasonal (summer–autumn and winter–spring) DOC concentrations (production) were delineated and related to discharge. Although antecedent temperature mainly determined the timing of switchover between periods of high DOC in the summer‐autumn and low DOC in winter‐spring, inter‐annual variability of export within the same season was largely dependent on its associated water flux. DOC fluxes ranged from 1·39 to 4·80 g m^?2 season^?1 during summer–autumn and 1·43 to 4·15 g m^?2 season^?1 in winter–spring.Relationships between DOC areal fluxes and catchment scale indicated that mainstem fluxes reflect the averaging of highly heterogeneous inputs from contrasting headwater catchments, leading to convergent DOC fluxes at catchment sizes of ca 100 km². However, during summer–autumn periods, in contrast to winter–spring, longitudinal mainstem DOC fluxes continue to decrease, most likely because of increasing biological processes. This highlights the importance of considering seasonal as well as annual changes in DOC fluxes with catchment scale. This study increases our understanding of the temporal variability of DOC upscaling patterns reflecting cumulative changes across different catchment scales and aids modelling of carbon budgets at different stages of riverine systems. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Variations in dissolved CO2 and CH4 in a first‐order stream and catchment: an investigation of soil–stream linkages

Spatial and seasonal variations in CO₂ and CH₄ concentrations in streamwater and adjacent soils were studied at three sites on Brocky Burn, a headwater stream draining a peatland catchment in upland Britain. Concentrations of both gases in the soil atmosphere were significantly higher in peat and riparian soils than in mineral soils. Peat and riparian soil CO₂ concentrations varied seasonally, showing a positive correlation with air and soil temperature. Streamwater CO₂ concentrations at the upper sampling site, which mostly drained deep peats, varied from 2·8 to 9·8 mg l^?1 (2·5 to 11·9 times atmospheric saturation) and decreased markedly downstream. Temperature‐related seasonal variations in peat and riparian soil CO₂ were reflected in the stream at the upper site, where 77% of biweekly variation was explained by an autoregressive model based on: (i) a negative log‐linear relationship with stream flow; (ii) a positive linear relationship with soil CO₂ concentrations in the shallow riparian wells; and (iii) a negative linear relationship with soil CO₂ concentrations in the shallow peat wells, with a significant 2‐week lag term. These relationships changed markedly downstream, with an apparent decrease in the soil–stream linkage and a switch to a positive relationship between stream flow and stream CO₂. Streamwater CH₄ concentrations also declined sharply downstream, but were much lower (<0·01 to 0·12 mg l^?1) than those of CO₂ and showed no seasonal variation, nor any relationship with soil atmospheric CH₄ concentrations. However, stream CH₄ was significantly correlated with stream flow at the upper site, which explained 57% of biweekly variations in dissolved concentrations. We conclude that stream CO₂ can be a useful integrative measure of whole catchment respiration, but only at sites where the soil–stream linkage is strong. Copyright © 2004 John Wiley & Sons, Ltd.     

Temperature in lowland Danish streams: contemporary patterns,empirical models and future scenarios

Continuous temperature measurements at 11 stream sites in small lowland streams of North Zealand, Denmark over a year showed much higher summer temperatures and lower winter temperatures along the course of the stream with artificial lakes than in the stream without lakes. The influence of lakes was even more prominent in the comparisons of colder lake inlets and warmer outlets and led to the decline of cold‐water and oxygen‐demanding brown trout. Seasonal and daily temperature variations were, as anticipated, dampened by forest cover, groundwater input, input from sewage plants and high downstream discharges. Seasonal variations in daily water temperature could be predicted with high accuracy at all sites by a linear air‐water regression model (r²: 0·903–0·947). The predictions improved in all instances (r²: 0·927–0·964) by a non‐linear logistic regression according to which water temperatures do not fall below freezing and they increase less steeply than air temperatures at high temperatures because of enhanced heat loss from the stream by evaporation and back radiation. The predictions improved slightly (r²: 0·933–0·969) by a multiple regression model which, in addition to air temperature as the main predictor, included solar radiation at un‐shaded sites, relative humidity, precipitation and discharge. Application of the non‐linear logistic model for a warming scenario of 4–5 °C higher air temperatures in Denmark in 2070‐2100 yielded predictions of temperatures rising 1·6–3·0 °C during winter and summer and 4·4–6·0 °C during spring in un‐shaded streams with low groundwater input. Groundwater‐fed springs are expected to follow the increase of mean air temperatures for the region. Great caution should be exercised in these temperature projections because global and regional climate scenarios remain open to discussion. Copyright © 2006 John Wiley & Sons, Ltd.     

Reconstructing long‐term records of dissolved CO2

The dissolved CO₂ concentration of stream waters is an important component of the terrestrial carbon cycle. This study reconstructs long‐term records of dissolved CO₂ concentration for the outlets of two large catchments (818 and 586 km²) in northern England. The study shows that:

• 1. The flux of dissolved CO₂ from the catchments (as carbon per catchment area), when adjusted for that which would be carried by the river water at equilibrium with the atmosphere, is between 0 and 0·39 t km⁻² year⁻¹ for the River Tees and between 0 and 0·65 t km⁻² year⁻¹ for the River Coquet.
• 2. The flux of dissolved CO₂ is closely correlated with dissolved organic carbon (DOC) export and is unrelated to dissolved CO₂ export from the headwaters of the study catchments.
• 3. The evasion rate of CO₂ from the rivers (as carbon per stream area) is between 0·0 and 1·49 kg m⁻² year⁻¹, and calculated in‐stream productions of CO₂ are estimated as between 0·5 and 2·5% of the stream evasion rate.
• 4. By mass balance, it is estimated that 8% of the annual flux of DOC is lost within the streams of the catchment.

The study shows that the loss of CO₂ from the streams of the Tees catchment is between 3·1 and 7·5 kt year⁻¹ (as carbon) for the River Tees, which is the same order as annual CH₄ flux from peats within the catchment and approximately 50% of the net CO₂ exchange to the peats of the catchment. Copyright © 2005 John Wiley & Sons, Ltd.     

The use of short‐lived radionuclides to quantify transitional bed material transport in a regulated river

We investigate the use of the short‐lived fallout radionuclide beryllium‐7 (⁷Be; t_1/2 = 53·4 days) as a tracer of medium and coarse sand (0·25–2 mm), which transitions between transport in suspension and as bed load, and evaluate the effects of impoundment on seasonal and spatial variations in bed sedimentation. We measure ⁷Be activities in approximately monthly samples from point bar and streambed sediments in one unregulated and one regulated stream. In the regulated stream our sampling spanned an array of flow and management conditions during the annual transition from flood control in the winter and early spring to run‐of‐the‐river operation from late spring to autumn. Sediment stored behind the dam during the winter quickly became depleted in ⁷Be activity. This resulted in a pulse of ‘dead’ sediment released when the dam gates were opened in the spring which could be tracked as it moved downstream. Measured average sediment transport velocities (30–80 metres per day (m d^?1)) exceed those typically reported for bulk bed load transport and are remarkably constant across varied flow regimes, possibly due to corresponding changes in bed sand fraction. Results also show that the length scale of the downstream impact of dam management on sediment transport is short (c. 1 km); beyond this distance the sediment trapped by the dam is replaced by new sediment from tributaries and other downstream sources. Copyright © 2006 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.     

Flow resistance in steep mountain streams

Resistance to flow at low to moderate stream discharge was examined in five small (12–77 km² drainage area) tributaries of Chilliwack River, British Columbia, more than half of which exhibit planar bed morphology. The resulting data set is composed of eight to 12 individual estimates of the total resistance to flow at 61 cross sections located in 13 separate reaches of five tributaries to the main river. This new data set includes 625 individual estimates of resistance to flow at low to moderate river stage. Resistance to flow in these conditions is high, highly variable and strongly dependent on stage. The Darcy–Weisbach resistance factor (ff) varies over six orders of magnitude (0·29–12 700) and Manning's n varies over three orders of magnitude (0·047–7·95). Despite this extreme range, both power equations at the individual cross sections and Keulegan equations for reach‐averaged values describe the hydraulic relations well. Roughness is divided into grain and form (considered as all non‐grain sources) components. Form roughness is the dominant component, accounting for about 90% of the total roughness of the system (i.e., form roughness is on average 8.6 times as great as grain roughness). Of the various quantitative and qualitative form‐roughness indicators observed, only the sorting coefficient (σ = D₈₄/D₅₀) correlates well with form roughness. Copyright © 2008 John Wiley & Sons, Ltd.     

Occurrence of phthalate diesters in rivers of the Paris district (France)

The occurrence and fate of six phthalate esters were investigated in the River Seine and two tributaries in the Paris area, at six sites from upstream to downstream, throughout different seasons, with special attention given to a flood episode. At all sites, except the River Marne, whatever the period, diethylhexyl phthalate (DEHP) displayed the highest concentration (0·323–0·779 µg l^?1 as mean values), followed by di‐n‐butyl phthalate (DnBP; 0·211–0·526 µg l^?1 as mean values), which is consistent with the production pattern. High phthalate concentrations appeared to be related to population density and industrial distribution. The strongest values were located downstream from wastewater treatment plant effluent inputs. Seasonal variations were closely related to river flow and air and water temperature. The annual evolution of phthalates was linked to the hydrological conditions. During the flood episode at Paris, the DEHP concentration displayed a sharp increase (260 to 1123 ng l^?1) occurring 9 days before the flood peak. The simultaneous fluctuations of NH₄, typical of domestic origin, and of DEHP suggests a similar origin from combined sewer overflows for both compounds. Other elevated values corresponded to the highest precipitation amounts, and demonstrated the contribution of non‐point‐source runoff and wastewater overflow to DEHP inputs. The DEHP concentration relationship with river flow displayed a clockwise hysteresis loop, corresponding to a ‘first‐flush’ effect in which the finite supplies are swept along in the early stage of the flood. Annual fluxes for 2004 at Paris were 2257 kg of DEHP and 1613 kg of DnBP. The flood period seemed to have a minor impact on annual phthalate transport (29·5% and 41% of the total for DEHP and for DnBP, respectively), which is contrary to annual suspended solids transport (69%). Copyright © 2007 John Wiley & Sons, Ltd.     

Fluvial carbon export and CO2 efflux in representative nested headwater catchments of the eastern La Plata River Basin

This study involved a baseline evaluation of fluvial carbon export and degas rates in three nested rural catchments (1 to 80 km²) in Taboão, a representative experimental catchment of the Upper Uruguay River Basin. Analyses of the carbon content in stream waters and the catchment carbon yield were based on 4‐year monthly in situ data and statistical modeling using the United States Geological Survey load estimator model. We also estimated p CO₂ and degas fluxes using carbonate equilibrium and gas‐exchange formulas. Our results indicated that the water was consistently p CO₂ saturated (~90% of the cases) and that the steep terrain favors high gas evasion rates. The mean calculated fluvial export was 5.4 tC·km^?2·year^?1 with inorganic carbon dominating (dissolved inorganic carbon:dissolved organic carbon ratio >4), and degas rates (~40 tC km^?2·year^?1) were nearly sevenfold higher than the downstream export. The homogeneous land use in this nested catchment system results in similar water‐quality characteristics, and therefore, export rates are expected to be closely related to the rainfall–runoff relationships at each scale. Although the sampling campaigns did not fully reproduce storm‐event conditions and related effects such as flushing or dilution of in‐stream carbon, our results indicated a potential link between dissolved inorganic carbon and slower hydrological pathways related to subsurface water storage and movement.     

Assessing sensitivity of hydrologic responses to climate change from forested watershed in Mississippi

The climatic processes such as changes in precipitation, temperature and atmospheric CO₂ concentration can intensify the effects on water resources. An assessment of the effects of long‐term climate change on water resources is essential to the development of water quality improvement programs. This study was conducted in the Upper Pearl River Watershed (UPRW) in east‐central Mississippi to assess the effects of long‐term potential future climate change on average mean monthly stream flow from the five spatially distributed U. S. Geological Survey (USGS) gage stations in the UPRW using the Soil and Water Assessment Tool. The model was calibrated (January 1981 to December 1994) and validated (January 1995 to September 2008) using monthly measured stream flow data. The calibrated and validated model determined good to very good performance for stream flow prediction (R² and E from 0·60 to 0·86) between measured and predicted stream flow values. The root mean square error values (from 14 to 37 m³ s^?1) were estimated at similar levels of errors during model calibration and validation. The results showed that long‐term (50 years) average monthly stream flow sensitivity due to climate change effects was found the greatest as a result of percentage change in the precipitation followed by carbon dioxide (CO₂) concentration and temperature. The long‐term model simulation scenarios as compared with the base scenario for all five spatially distributed USGS gage stations in the UPRW estimated an average monthly stream flow decrease (from 54 to 67%) and average monthly stream flow increase (from 67 to 79%) depending on the spatial characteristics of the USGS gage stations. Overall, the results indicate that the UPRW hydrology is very sensitive to potential future climate changes and that these changes could stimulate increased streamflow generation from the watershed. Copyright © 2010 John Wiley & Sons, Ltd.     

Temporal cycles of karst denudation in northwest Georgia,U.S.A.

Time patterns of karst denudation in northwest Georgia (U.S.A.) were investigated at three spring sites for 12 months and at five stream sites for 10 years. Rainfall was evenly distributed and showed no significant seasonality. At the springs, as well as the streams, water hardness was largely controlled by discharge. At the springs, soil pCO₂ and water pH were strongly correlated (r + -0·69 to -0·83). Solute transport in spring waters was highly seasonal, with two conduit flow springs removing more limestone in the winter, and the diffuse flow spring removing more during the growing season. At the stream sites, most denudation occurred during the winter and spring seasons, and least during the summer. Fourier analysis showed that variations in denudation occur on deterministic (long-wave) as well as stochastic (shortwave) time scales. As contributing variables, discharge varied in short-wave and long-wave cycles, whereas soil pCO₂ showed only a long-wave cycle. The 12 month deterministic cycles were the most important, with changes in discharge taking precedence over soil pCO₂. Time series regression explains up to 69 per cent of changes in denudation through rain and soil pCO₂. Time cycles in available water are the key controlling factor of denudation, and amounts of available soil CO₂ may not be as important in the temporal patterns of karst downwearing as has been believed previously.     

Artificial neural network models for estimating regional reference evapotranspiration based on climate factors

Evapotranspiration (ET) is one of the basic components of the hydrologic cycle and is essential for estimating irrigation water requirements. In this study, an artificial neural network (ANN) model for reference evapotranspiration (ET₀) calculation was investigated. ANNs were trained and tested for arid (west), semi‐arid (middle) and sub‐humid (east) areas of the Inner Mongolia district of China. Three or four climate factors, i.e. air temperature (T), relative humidity (RH), wind speed (U) and duration of sunshine (N) from 135 meteorological stations distributed throughout the study area, were used as the inputs of the ANNs. A comparison was conducted between the estimates provided by the ANNs and by multilinear regression (MLR). The results showed that ANNs using the climatic data successfully estimated ET₀ and the ANNs simulated ET₀ better than the MLRs. The ANNs with four inputs were more accurate than those with three inputs. The errors of the ANNs with four inputs were lower (with RMSE of 0·130 mm d^?1, RE of 2·7% and R² of 0·986) in the semi‐arid area than in the other two areas, but the errors of the ANNs with three inputs were lower in the sub‐humid area (with RMSE of 0·21 mm d^?1, RE of 5·2% and R² of 0·961. For the different seasons, the results indicated that the highest errors occurred in September and the lowest in April for the ANNs with four inputs. Similarly, the errors were higher in September for the ANNs with three inputs. Copyright © 2008 John Wiley & Sons, Ltd.     

Hydraulic characteristics of a small Coastal Plain stream of the southeastern United States: effects of hydrology and season

Various physical and biological properties affect solute transport patterns in streams. We measured hydraulic characteristics of Payne Creek, a low‐gradient upper Coastal Plain stream, using tracer experiments and parameter estimation with OTIS‐P (one‐dimensional transport with inflow and storage with parameter optimization). The primary objective of this study was to estimate the effects of varying discharge, season, and litter accumulation on hydraulic parameters. Channel area A ranged from 0·081 to 0·371 m² and transient storage area A_s ranged from 0·027 to 0·111 m². Dispersion D ranged from 1·5 to 11·1 m² min⁻¹ and exchange coefficient α ranged from 0·009 to 0·038 min⁻¹. Channel area and dispersion were positively correlated to discharge Q, whereas storage area and exchange coefficient were not. Relative storage size A_s/A ranged from 0·17 to 0·59, and was higher during fall than other seasons under a similar Q. The fraction of median travel time due to transient storage ranged from 8·8 to 34·5% and was significantly correlated with Q through a negative power function. Both metrics indicated that transient storage was a significant component affecting solute transport in Payne Creek, especially during the fall. Comparison between the measured channel area A_c and A suggested that surface storage was dominant in Payne Creek. During fall, accumulation of leaf litter resulted in larger A and A_s and lower velocity and D than during other seasons with similar discharge. Seasonal changes in discharge and organic matter accumulation, and dynamic channel morphology affected the magnitude of transient storage and overall hydraulic characteristics of Payne Creek. Copyright © 2005 John Wiley & Sons, Ltd.     

Water and nutrient fluxes in a cool temperate rainforest at the Cordillera de la Costa in southern Chile

Water and nutrient fluxes were studied during a 12-month period in an alerce (Fitzroya cupressoides) forest, located in a remote site at the Cordillera de la Costa (40°05′S) in southern Chile. Measurements of precipitation, throughfall, stemflow, effective precipitation, soil infiltration and stream flow were carried out in an experimental, small watershed. Simultaneously, monthly water samples were collected to determine the concentrations and transport of organic-N, NO₃-N, total-P, K⁺, Ca²⁺, Na⁺ and Mg²⁺ in all levels of forest. Concentration of organic-N, NO₃-N, total-P and K⁺ showed a clear pattern of enrichment in the throughfall, stemflow, effective precipitation and soil infiltration. For Ca²⁺ and Mg²⁺, enrichment was observed in the effective precipitation, soil infiltration and stream flow. Annual transport of K⁺, Na⁺, Ca²⁺ and Mg²⁺ showed that the amounts exported from the forest via stream flow (K⁺=0·95, Na⁺=32·44, Ca²⁺=8·76 and Mg²⁺=7·16 kg ha⁻¹ yr⁻¹) are less than the inputs via precipitation (K⁺=6·39, Na⁺=40·99, Ca²⁺=15·13 and Mg²⁺=7·61 kg ha⁻¹ yr⁻¹). The amounts of organic-N and NO₃-N exported via stream flow (organic-N=1·04 and No₃-N=3·06 kg ha⁻¹ yr⁻¹) were relatively small; however, they represented greater amounts than the inputs via precipitation (organic-N=0·74 and NO₃-N=0·97 kg ha⁻¹ yr⁻¹), because of the great contribution of this element in the superficial soil horizon, where the processes of decomposition of organic material, mineralization and immobilization of the nutrients occurs. © 1998 John Wiley & Sons, Ltd.     

Stable isotope tracers as diagnostic tools in upscaling flow path understanding and residence time estimates in a mountainous mesoscale catchment

δ¹⁸O measurements of precipitation and stream waters were used as a natural tracer to investigate hydrological pathways and residence times in the River Feshie, a complex mesoscale (231 km²) catchment in the Cairngorm Mountains of Scotland. Precipitation δ¹⁸O exhibited strong seasonal variation over the 2001–02 hydrological year, ranging from −6·9‰ in the summer, to −12·0‰ during winter snowfalls (mean δ¹⁸O −9·59‰). Although damped, this seasonality was reflected in stream water outputs at seven sampling sites in the catchment, allowing δ¹⁸O variations to be used to infer hydrological source areas. Thus, stream water δ¹⁸O was generally controlled by a seasonally variable storm flow end member, mixing with groundwater of more constant isotopic composition. Periodic regression analysis allowed the differences in this mixing process between monitoring subcatchments to be assessed more quantitatively to provide a preliminary estimate of mean stream water residence time. This demonstrated the importance of responsive hydrological pathways associated with peat and shallow alpine soils in the headwater subcatchments in producing seasonally variable runoff with short mean residence times (33–113 days). In contrast, other tributaries with more freely draining soils and larger groundwater storage in shallow aquifers provided more effective mixing of variable precipitation inputs, resulting in longer residence time estimates (178–445 days). The mean residence time of runoff leaving the Feshie catchment reflected an integration of these contrasting influences (110–200 days). These insights from δ¹⁸O measurements extend the hydrological understanding of the Feshie catchment gained from other hydrochemical tracers, and demonstrate the utility of isotope tracers in investigating hydrological processes at the mesoscale. Copyright © 2005 John Wiley & Sons, Ltd.     

Factors controlling the chemical evolution of travertine‐depositing rivers of the Barkly karst,northern Australia

Groundwaters feeding travertine‐depositing rivers of the northeastern segment of the Barkly karst (NW Queensland, Australia) are of comparable chemical composition, allowing a detailed investigation of how the rate of downstream chemical evolution varies from river to river. The discharge, pH, temperature, conductivity and major‐ion concentrations of five rivers were determined by standard field and laboratory techniques. The results show that each river experiences similar patterns of downstream chemical evolution, with CO₂ outgassing driving the waters to high levels of calcite supersaturation, which in turn leads to widespread calcium carbonate deposition. However, the rate at which the waters evolve, measured as the loss of CaCO₃ per kilometre, varies from river to river, and depends primarily upon discharge at the time of sampling and stream gradient. For example, Louie Creek (Q = 0·11 m³ s^?1) and Carl Creek (Q = 0·50 m³ s^?1) have identical stream gradients, but the loss of CaCO₃ per kilometre for Louie Creek is twice that of Carl Creek. The Gregory River (Q = 3·07 m³ s^?1), O'Shanassy River (Q = 0·57 m³ s^?1) and Lawn Hill Creek (Q = 0·72 m³ s^?1) have very similar gradients, but the rate of hydrochemical evolution of the Gregory River is significantly less than either of the other two systems. The results have major implications for travertine deposition: the stream reach required for waters to evolve to critical levels of calcite supersaturation will, all others things being equal, increase with increasing discharge, and the length of reach over which travertine is deposited will also increase with increasing discharge. This implies that fossil travertine deposits preserved well downstream of modern deposition limits are likely to have been formed under higher discharge regimes. Copyright © 2002 John Wiley & Sons, Ltd.     

Influences of catchment characteristics on nitrogen concentration in largely forested streams during the base flow period

Based on measured stream nitrogen concentrations at outlets of 12 small sub‐areas (1·3–54·7 km²) in a largely forested catchment during the base flow period, we investigated the influences of discharges and different catchment characteristics on stream nitrogen concentration. Our field surveys were carried out during the 11‐month's period from April 2001 to February 2002 and the correlations between nitrogen concentrations and catchment characteristics were studied. The results showed that the vegetation cover was strongly correlated to total nitrogen (TN) and nitrate + nitrite ? nitrogen (NO_x‐N) concentrations. That is, the TN and NO_x‐N concentrations had positive correlations with mean normalized difference vegetation cover index (NDVI) of each sub‐area during dormant seasons (mean NDVI < 0 · 70) and had negative correlations during the growing season (mean NDVI ≥ 0 . 70). The significance of catchment characteristics to TN and NO_x‐N concentrations was ranked as vegetation cover > soil > topography > land use, and the best models can account for 55–64% of the variance of TN and NO_x‐N concentrations. Copyright © 2006 John Wiley & Sons, Ltd.