Correlating specific conductivity with total hardness in limestone and dolomite karst waters

Under field conditions modern digital conductivity meters give standardized, rapid and reproducible measurements. Here we investigate the accuracy of their estimates of the composition of karst waters, as total hardness (TH, as mg/L CaCO₃) for limestone and dolomite. These are the fundamental measures of process in carbonate karst geomorphology. PHREEQC theoretical curves for the dissolution of pure calcite/aragonite and dolomite in water at 25 °C are compared with water analyses from karst studies worldwide. Other principal ions encountered are sulphates, nitrates and chlorides (the ‘SNC’ group). From carbonate karsts, 2309 spring, well and stream samples were divided into uncontaminated (SNC < 10%), moderately contaminated (10 < SNC < 20%), and contaminated (SNC > 20%) classes. Where specific conductivity (SpC) is less than 600 µS/cm, a clear statistical distinction can be drawn between waters having little contamination and substantially contaminated waters with SNC > 20%. As sometimes claimed in manufacturers' literature, in ‘clean’ limestone waters TH is close to ¹/2SpC, with a standard error of 2–3 mg/L. The slope of the best‐fit line for 1949 samples covering all SNC classes where SpC < 600 µS/cm is 1·86, very close to the 1·88 obtained for clean limestone waters; however, the value of the intercept is ten times higher. The regression line for clean limestone waters where SpC > 600 µS/cm helps to distinguish polluted waters from clean waters with possible endogenic sources of CO₂. In the range 250 < SpC < 600 µS/cm, dolomite waters can be readily distinguished from limestone waters. Copyright © 2005 John Wiley & Sons, Ltd.     

Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological,chemical and isotopic approach

Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north‐eastern USA. Chemical, isotopic and hydrological responses with particular emphasis on S dynamics were evaluated for Archer Creek (New York), Sleepers River (Vermont) and Cone Pond (New Hampshire) watersheds. From 1 August to 14 September 2002, all three watersheds had very low precipitation (48 to 69 mm) resulting in either very low or no discharge (mean 0·015, 0·15 and 0·000 mm day^?1 for Archer Creek, Sleepers River and Cone Pond, respectively). From 15 September to 31 October 2002, there was a substantial increase in precipitation totals (212, 246 and 198 mm, respectively) with increased discharge. Archer Creek was characterized by a large range of SO₄^2? concentrations (152 to 389 µeq L^?1, mean = 273 µeq L^?1) and also exhibited the greatest range in δ³⁴S values of SO₄^2? (?1·4 to 8·8 ‰ ). Sleepers River's SO₄^2? concentrations ranged from 136 to 243 µeq L^?1 (mean = 167 µeq L^?1) and δ³⁴S values of SO₄^2? ranged from 4·0 to 9·0 ‰ . Cone Pond's SO₄^2? concentrations (126–187 µeq L^?1, mean = 154 µeq L^?1) and δ³⁴S values (2·4 to 4·3 ‰ ) had the smallest ranges of the three watersheds. The range and mean of δ¹⁸O‐SO₄^2? values for Archer Creek and Cone Pond were similar (3·0 to 8·9 ‰ , mean = 4·5 ‰ ; 3·9 to 6·3 ‰ , mean = 4·9 ‰ ; respectively) while δ¹⁸O‐SO₄^2? values for Sleepers River covered a larger range with a lower mean (1·2 to 10·0 ‰ , mean = 2·5). The difference in Sleepers River chemical and isotopic responses was attributed to weathering reactions contributing SO₄^2?. For Archer Creek wetland areas containing previously reduced S compounds that were reoxidized to SO₄^2? probably provided a substantial source of S. Cone Pond had limited internal S sources and less chemical or isotopic response to storms. Differences among the three watersheds in S biogeochemical responses during these storm events were attributed to differences in S mineral weathering contributions, hydrological pathways and landscape features. Further evaluations of differences and similarities in biogeochemical and hydrological responses among watersheds are needed to predict the impacts of climate change. Copyright © 2008 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.     

Hydrological heterogeneity of an alpine stream–lake network in Switzerland

Water source and lake landscape position can strongly influence the physico‐chemical characteristics of flowing waters over space and time. We examined the physico‐chemical heterogeneity in surface waters of an alpine stream‐lake network (>2600 m a.s.l.) in Switzerland. The catchment comprises two basins interspersed with 26 cirque lakes. The larger lakes in each basin are interconnected by streams that converge in a lowermost lake with an outlet stream. The north basin is primarily fed by precipitation and groundwater, whereas the south basin is fed mostly by glacial melt from rock glaciers. Surface flow of the entire channel network contracted by ～60% in early autumn, when snowmelt runoff ceased and cold temperatures reduced glacial outputs, particularly in the south basin. Average water temperatures were ～4 °C cooler in the south basin, and temperatures increased by about 4–6 °C along the longitudinal gradient within each basin. Although overall water conductivity was low (<27 µS cm^?1) because of bedrock geology (ortho‐gneiss), the south basin had two times higher conductivity values than the north basin. Phosphate‐phosphorus levels were below analytical detection limits, but particulate phosphorus was about four times higher in the north basin (seasonal average: 9 µg l^?1) than in the south basin (seasonal average: 2 µg l^?1). Dissolved nitrogen constituents were around two times higher in the south basin than in the north basin, with highest values averaging > 300 µg l^?1 (nitrite + nitrate‐nitrogen), whereas particulate nitrogen was approximately nine times greater in the north basin (seasonal average: 97 µg l^?1) than in the south basin (seasonal average: 12 µg l^?1). Total inorganic carbon was low (usually <0·8 mg l^?1), silica was sufficient for algal growth, and particulate organic carbon was 4·5 times higher in the north basin (average: 0·9 mg l^?1) than in the south basin (average: 0·2 mg l^?1). North‐basin streams showed strong seasonality in turbidity, particulate‐nitrogen and ‐phosphorus, and particulate organic carbon, whereas strong seasonality in south‐basin streams was observed in conductivity and dissolved nitrogen. Lake position influenced the seasonal dynamics in stream temperatures and nutrients, particularly in the groundwater/precipitation‐fed north‐basin network. Copyright © 2007 John Wiley & Sons, Ltd.     

The effect of hydrochemical factors on the dissolution rate of gypsiferous rocks in flowing water

In order to investigate the rate of dissolution of gypsiferous rocks under natural conditions in streams of the Ebro river basin, 55 dissolution trials were carried out with spheres of alabastrine gypsum placed in flowing water. Experimental conditions involved flow velocities between 0·3 and 1·2 m s^?1, electrical conductivities between 0·3 and 1·9 dS m^?1, and the saturation indices of gypsum between ?2·1 and ?0·33. Mean values of dissolution rate obtained vary from 104 to 226 gm^?2 h^?1. This loss of mass corresponded to a volume of gypsum of between 393 and 853mmm^?2 year^?1. The factors most affecting the dissolution of gypsum are in descending order of importance: flow velocity > electrical conductivity > gypsum saturation.     

Nitrate content and potential microbial signature of rock glacier outflow,Colorado Front Range

Here we characterize the nutrient content in the outflow of the Green Lake 5 rock glacier, located in the Green Lakes Valley of the Colorado Front Range. Dissolved organic carbon (DOC) was present in all samples with a mean concentration of 0·85 mg L^?1 . A one‐way analysis of variance test shows no statistical difference in DOC amounts among surface waters (p = 0·42). Average nitrate concentrations were 69 µmoles L^?1 in the outflow of the rock glacier, compared to 7 µmoles L^?1 in snow and 25 µmoles L^?1 in rain. Nitrate concentrations from the rock glacier generally increased with time, with maximum concentrations of 135 µmoles L^?1 in October, among the highest nitrate concentrations reported for high‐elevation surface waters. These high nitrate concentrations appear to be characteristic of rock glacier outflow in the Rocky Mountains, as a paired‐difference t‐test shows that nitrate concentrations from the outflow of 7 additional rock glaciers were significantly greater compared to their reference streams (p = 0·003). End‐member mixing analysis suggest that snow was the dominant source of nitrate in June, ‘soil’ solution was the dominant nitrate source in July, and base flow was the dominant source in September. Fluoresence index values and PARAFAC analyses of dissolved organic matter (DOM) are also consistent with a switch from terrestrial DOM in the summer time period to an increasing aquatic‐like microbial source during the autumn months. Copyright © 2006 John Wiley & Sons, Ltd.     

Wetland nitrogen dynamics in an Adirondack forested watershed

Wetlands often form the transition zone between upland soils and watershed streams, however, stream–wetland interactions and hydrobiogeochemical processes are poorly understood. We measured changes in stream nitrogen (N) through one riparian wetland and one beaver meadow in the Archer Creek watershed in the Adirondack Mountains of New York State, USA from 1 March to 31 July 1996. In the riparian wetland we also measured changes in groundwater N. Groundwater N changed significantly from tension lysimeters at the edge of the peatland to piezometer nests within the peatland. Mean N concentrations at the peatland perimeter were 1·5, 0·5 and 18·6 µmol L^?1 for NH₄⁺, NO₃^? and DON (dissolved organic nitrogen), respectively, whereas peatland groundwater N concentration was 56·9, 1·5 and 31·6 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively. The mean concentrations of stream water N species at the inlet to the wetlands were 1·5, 10·1 and 16·9 µmol L^?1 for NH₄⁺, NO₃^? and DON, respectively and 1·6, 28·1 and 8·4 µmol L^?1 at the wetland outlet. Although groundwater total dissolved N (TDN) concentrations changed more than stream water TDN through the wetlands, hydrological cross‐sections for the peatland showed that wetland groundwater contributed minimally to stream flow during the study period. Therefore, surface water N chemistry was affected more by in‐stream N transformations than by groundwater N transformations because the in‐stream changes, although small, affected a much greater volume of water. Stream water N input–output budgets indicated that the riparian peatland retained 0·16 mol N ha^?1 day^?1 of total dissolved N and the beaver meadow retained 0·26 mol N ha^?1 day^?1 during the study period. Nitrate dominated surface water TDN flux from the wetlands during the spring whereas DON dominated during the summer. This study demonstrates that although groundwater N changed significantly in the riparian peatland, those changes were not reflected in the stream. Consequently, although in‐stream changes of N concentrations were less marked than those in groundwater, they had a greater effect on stream water chemistry—because wetland groundwater contributed minimally to stream flow. Copyright © 2004 John Wiley & Sons, Ltd.     

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.     

The effect of drawdown on suspended solids and phosphorus export from Columbia Lake,Waterloo, Canada

This study examines the effect of drawdown on the timing and magnitude of suspended solids and associated phosphorus export from a 12 ha reservoir located in an urbanized watershed in southern Ontario, Canada. Water level in Columbia Lake was lowered by 1·15 m over a 2‐week period in November 2001. The total phosphorus (TP) concentrations ranged from 63 to 486 µg L^?1 in Columbia Lake and 71 to 373 µg L^?1 at its outflow. All samples exceeded the Provincial Water Quality Objective of 30 µg TP L^?1. Outflow concentrations of suspended solids and TP increased significantly with decreasing lake level and were attributed to the resuspension of cohesive bottom sediments that occurred at a critical threshold lake level (0·65 m below summer level). Suspended solids at the outflow consisted of flocculated cohesive materials with a median diameter (D₅₀) of c. 5 µm. Particulate organic carbon accounted for 8·5% of the suspended solids export by mass. A total mass of 18·5 t of suspended solids and 62·6 kg TP was exported from Columbia Lake, which represents a significant pulse of sediment‐associated P to downstream environments each autumn during drawdown. The downstream impacts of this release can be minimized if the water level in Columbia Lake is lowered no more than 0·5 m below summer levels. Copyright © 2004 John Wiley & Sons, Ltd.     

Geochemistry of meteoric diagenesis in carbonate islands of the northern Bahamas: 2. Geochemical modelling and budgeting of diagenesis

Geochemical characterization and numerical modelling of surface water and ground water, combined with hydrological observations, provide quantitative estimates of meteoric diagenesis in Pleistocene carbonates of the northern Bahamas. Meteoric waters equilibrate with aragonite, but water‐ rather than mineral‐controlled reactions dominate. Dissolutional lowering of the undifferentiated bedrock surface is an order of magnitude slower than that within soil‐filled topographic hollows, generating small‐scale relief at a rate of 65–140 mm ka^?1 and a distinctive pocketed topography. Oxidation of organic matter within the subsoil and vadose zones generates an average P of 4·0 × 10^?3 atm, which drives dissolution during vadose percolation and/or at the water table. However, these dissolution processes together account for <60% of the average rock‐derived calcium in groundwaters pumped from the freshwater lens. The additional calcium may derive from oxidation of organic carbon within the lens, accounting for the high P of the lens waters. Mixing between meteoric waters of differing chemistry is diagenetically insignificant, but evapotranspiration from the shallow water table is an important drive for subsurface cementation. Porosity generation in the shallow vadose zone averages 1·6–3·2% ka^?1. Phreatic meteoric diagenesis is focused near the water table, where dissolution generates porosity at 1·4–2·8% ka^?1. Maximum dissolution rates, however, are similar to those of evaporation‐driven precipitation, which occludes porosity of 4·0 ± 0·6% ka^?1. This drives porosity inversion, from primary interparticle to secondary mouldic, vug and channel porosity. In the deeper freshwater lens, oxidation of residual organic carbon and reoxidation of reduced sulphur species from deeper anaerobic oxidation of organic carbon may generate porosity up to 0·06% ka^?1. Meteoric diagenesis relies critically on hydrological routing and vadose thickness (controlled by sea level), as well as the geochemical processes active. A thin vadose zone permits direct evaporation from the water table and drives precipitation of meteoric phreatic cements even where mineral stabilization is complete. Copyright © 2007 John Wiley & Sons, Ltd.     

Zur ökonomischen Bedeutung der biologischen Selbstreinigung

In twelve flowing water (Q 1.04… 30.4 m³/s, 0.5… 1.2 m/s) the self-purification efficiency in 110 river sections (L 1.3… 26.4 km) is determined as the load difference in kg · d^?1 COD-Mn as well as in g · m^?3 referred to the daily passage. In the economical comparison, the self-purification efficiency is valued as substitution for wastewater treatment plants of the same capacity. At a mean specific capacity of 8.6 g · m^?3, the self-purification efficiency of the investigated waters is equivalent to economical values of 124 · 10³… 534 · 10³ M km^?1 investment costs, 11 · 10³… 80 · 10³ M · a^?1km^?1 operating costs and 5… 81 MWh · a^?1 km^?1 expenditure of energy. The specific capacity in g · m^?3 COD-Mn shows an exponential regression to the degree of saprobity (L = 0.015 · exp (1.7358 · S)). From this empirical model the limits of the self-purification capacity of aerobic waters by oxygen input can be detected: in respective examples more than 50% of the required oxygen input are due to weirs.     

The solute budget of a forest catchment and solute fluxes within a Pinus radiata and a secondary native forest site,southern Chile

Solute concentrations and fluxes in rainfall, throughfall and stemflow in two forest types, and stream flow in a 90 ha catchment in southern Chile (39°44′S, 73°10′W) were measured. Bulk precipitation pH was 6·1 and conductivity was low. Cation concentrations in rainfall were low (0·58 mg Ca²⁺ l^?1, 0·13 mg K⁺ l^?1, 0·11 mg Mg²⁺ l^?1 and <0·08 mg NH₄–N l^?1), except for sodium (1·10 mg l^?1). Unexpected high levels of nitrate deposition in rainfall (mean concentration 0·38 mg NO₃–N l^?1, total flux 6·3 kg NO₃–N ha^?1) were measured. Concentrations of soluble phosphorous in bulk precipitation and stream flow were below detection limits (<0·09 mg l^?1) for all events. Stream‐flow pH was 6·3 and conductivity was 28·3 μs. Stream‐water chemistry was also dominated by sodium (2·70 mg l^?1) followed by Ca, Mg and K (1·31, 0·70 and 0·36 mg l^?1). The solute budget indicated a net loss of 3·8 kg Na⁺ ha^?1 year^?1, 5·4 kg Mg²⁺ ha^?1 year^?1, 1·5 kg Ca²⁺ ha^?1 year^?1 and 0·9 kg K⁺ ha^?1 year^?1, while 4·9 kg NO₃–N ha^?1 year^?1 was retained by the ecosystem. Stream water is not suitable for domestic use owing to high manganese and, especially, iron concentrations. Throughfall and stemflow chemistry at a pine stand (Pinus radiata D. Don) and a native forest site (Siempreverde type), both located within the catchment, were compared. Nitrate fluxes within both forest sites were similar (1·3 kg NO₃–N ha^?1 year^?1 as throughfall). Cation fluxes in net rainfall (throughfall plus stemflow) at the pine stand generally were higher (34·8 kg Na⁺ ha^?1 year^?1, 21·5 kg K⁺ ha^?1 year^?1, 5·1 kg Mg²⁺ ha^?1 year^?1) compared with the secondary native forest site (24·7 kg Na⁺ ha^?1 year^?1, 18·9 kg K⁺ ha^?1 year^?1 and 4·4 kg Mg²⁺ ha^?1 year^?1). However, calcium deposition beneath the native forest stand was higher (15·9 kg Ca²⁺ ha^?1 year^?1) compared with the pine stand (12·6 kg Ca²⁺ ha^?1 year^?1). Copyright © 2002 John Wiley & Sons, Ltd.     

Evaluating nitrate uptake in a Rocky Mountain stream using labelled 15N and ambient nitrate chemistry

Background aqueous chemistry and ¹⁵N_nitrate tracer injection methods were used to calculate in‐stream nitrate uptake metrics at Red Canyon Creek, a third‐order stream in the Rocky Mountains in the state of Wyoming, United States. ‘Net’ nitrate uptake lengths, which reflect both nitrate uptake and regeneration, and ‘gross’ nitrate uptake lengths, which exclude re‐mineralization, were quantified separately from background nitrate chemistry and ¹⁵N labelling tracer data, respectively. Gross nitrate uptake lengths, from tracer injections of ¹⁵N labelled nitrate, ranged from 502 to 3140 m. Net nitrate uptake lengths, from background nitrate chemistry downstream of a point source, ranged from 1170 to 4330 m. Diurnal changes in uptake lengths suggest the importance of nitrate utilization by autotrophs in the stream and benthic zone. The differences between net and gross nitrate uptake lengths along lower reaches of Red Canyon Creek allowed us to estimate the nitrate regeneration rate, which was 0·056–0·080 µmol m^?2 s^?1 during the day and 0·0062–0·0083 µmol m^?2 s^?1 at night. Spatial patterns of streambed pore water chemistry indicate those areas of the hyporheic zone where denitrification was likely occurring. Permanent log dams generated stronger redox gradients in the hyporheic zone than areas with transient beaver dams. By combining isotopically labelled nitrate additions, estimates of uptake from background aqueous nitrate chemistry and characterization of redox conditions in the hyporheic zone, we were able to determine the nitrate regeneration rate and the redox processes responsible for nitrogen cycling in the hyporheic zone. Copyright © 2010 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.     

Relationship of topography to surface water chemistry with particular focus on nitrogen and organic carbon solutes within a forested watershed in Hokkaido,Japan

We studied the relationships between streamwater chemistry and the topography of subcatchments in the Dorokawa watershed in Hokkaido Island, northern Japan, to examine the use of topography as a predictor of streamwater chemistry in a watershed with relatively moderate terrain compared with other regions of Japan. Topographic characteristics of the Dorokawa watershed and its subcatchments were expressed as topographic index (TI) values, which ranged from 4·5 to 20·4 for individual grid cells (50 × 50 m²), but averaged from 6·4 to 7·4 for the 20 subcatchments. Streamwater samples for chemical analyses were collected four times between June and October 2002 from 20 locations in the watershed. The pH of water that passed through the watershed increased from ～5·0 to 7·0, with major increases in Na⁺ and Ca²⁺ and marked decreases in NO₃^? and SO . Distinctive spatial patterns were observed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and NO₃^? concentrations of streamwater across the watershed. Statistical analyses indicated significant linear relationships between the average TI values of subcatchments and DOC, DON, and NO₃^? concentrations. Furthermore, the proportion of DOC in streamwaters in the wet season increased with TI values relative to other nitrogen species, whereas NO₃^? concentrations decreased with TI. The gradients of soil wetness and the presence of wetlands explained many of the observed spatial and temporal patterns of DOC, DON, and NO₃^? concentrations in the surface waters of the Dorokawa watershed. Our results suggest that the TI is especially useful for predicting the spatial distribution of DOC, DON and NO₃^? in the surface waters of Hokkaido, where topographical relief is moderate and wetlands more common than in other regions of Japan. Copyright © 2006 John Wiley & Sons, Ltd.     

Solute movement through intact columns of cryoturbated Upper Chalk

Cryoturbated Upper Chalk is a dichotomous porous medium wherein the intra‐fragment porosity provides water storage and the inter‐fragment porosity provides potential pathways for relatively rapid flow near saturation. Chloride tracer movement through 43 cm long and 45 cm diameter undisturbed chalk columns was studied at water application rates of 0·3, 1·0, and 1·5 cm h^?1. Microscale heterogeneity in effluent was recorded using a grid collection system consisting of 98 funnel‐shaped cells each 3·5 cm in diameter. The total porosity of the columns was 0·47 ± 0·02 m³ m^?3, approximately 13% of pores were ≥ 15 µm diameter, and the saturated hydraulic conductivity was 12·66 ± 1·31 m day^?1. Although the column remained unsaturated during the leaching even at all application rates, proportionate flow through macropores increased as the application rate decreased. The number of dry cells (with 0 ml of effluent) increased as application rate decreased. Half of the leachate was collected from 15, 19 and 22 cells at 0·3, 1·0, 1·5 cm h^?1 application rates respectively. Similar breakthrough curves (BTCs) were obtained at all three application rates when plotted as a function of cumulative drainage, but they were distinctly different when plotted as a function of time. The BTCs indicate that the columns have similar drainage requirement irrespective of application rates, as the rise to the maxima (C/C_o) is almost similar. However, the time required to achieve that leaching requirement varies with application rates, and residence time was less in the case of a higher application rate. A two‐region convection–dispersion model was used to describe the BTCs and fitted well (r² = 0·97–0·99). There was a linear relationship between dispersion coefficient and pore water velocity (correlation coefficient r = 0·95). The results demonstrate the microscale heterogeneity of hydrodynamic properties in the Upper Chalk. Copyright © 2007 John Wiley & Sons, Ltd.     

Groundwater quality in Mesogea basin in eastern Attica (Greece)

Studies on the hydrogeological conditions of the Mesogea basin in east Attica reveal that the aquifers developed on the post‐alpine formations at the inner part of the coastal brackish zone exhibit positive hydraulic head. These Neogene and Quaternary deposits present high salt concentrations. Selected points were sampled (total 85: 51 wells and 34 boreholes) in order to obtain hydrogeological and hydrochemical data for a better understanding of the structure, operation and dynamics of the aquifer of the area. Statistical methods, R‐mode factor analysis and scatter‐plot diagrams were used for the hydrochemical analysis and presentation of the data. The groundwater resources are relatively weak and there is significant quality degradation due to the geological structure of the greater area, as well as the bad management of the aquifer and anthropogenic activities. Groundwater is characterized by high salt concentrations. Electrical conductivity values range between 260 and 6970 µS cm^?1. High salt concentrations at the coastal aquifers are due to sea intrusion, whereas they are attributed to the dissolution of minerals of the geological environment in the inland area. The groundwaters of the study area can be classified into five water types: Ca–HCO₃, Mg–HCO₃, Na–HCO₃, Na–Cl and Mg–Cl. They are saturated in dolomite and calcite, whereas they are unsaturated in anhydrite. High ion concentrations, e.g. ] (0‐221 mg l^?1), ] (0·01‐1·88 mg l^?1), ] (0·01‐6·75 mg l^?1), as well as high heavy metals concentrations are attributed to anthropogenic impacts. Copyright © 2006 John Wiley & Sons, Ltd.     

Landscape influences on aluminium and dissolved organic carbon in streams draining the Hubbard Brook valley,New Hampshire,USA

Concentrations of both aluminium (Al) and dissolved organic carbon (DOC) in stream waters are likely to be regulated by factors that influence water flowpaths and residence times, and by the nature of the soil horizons through which waters flow. In order to investigate landscape‐scale spatial patterns in streamwater Al and DOC, we sampled seven streams draining the Hubbard Brook valley in central New Hampshire. We observed considerable variation in stream chemistry both within and between headwater watersheds. Across the valley, concentrations of total monomeric aluminium (Al_m) ranged from below detection limits (<0·7 µmol l⁻¹) to 22·3 µmol l⁻¹. In general, concentrations of Al_m decreased as pH increased downslope. There was a strong relationship between organic monomeric aluminium (Al_o) and DOC concentrations (R² = 0·92). We observed the highest Al_m concentrations in: (i) a watershed characterized by a steep narrow drainage basin and shallow soils and (ii) a watershed characterized by exceptionally deep forest floor soils and high concentrations of DOC. Forest floor depth and drainage area together explained much of the variation in ln Al_m (R² = 0·79; N = 45) and ln DOC (R² = 0·87; N = 45). Linear regression models were moderately successful in predicting ln Al_m and ln DOC in streams that were not included in model building. However, when back‐transformed, predicted DOC concentrations were as much as 72% adrift from observed DOC concentrations and Al_m concentrations were up to 51% off. This geographic approach to modelling Al and DOC is useful for general prediction, but for more detailed predictions, process‐level biogeochemical models are required. Copyright © 2005 John Wiley & Sons, Ltd.     

Distribution Study of U,V, Mo,and Zr in Different Sites of Lakes Van and Hazar,River and Seawater Samples by ICP‐MS

The aim of this study is to investigate the concentrations of U, Th, V, Mo, and Zr in natural waters taken from Turkey. Among these water species, Lake Van is the largest soda lake and the fourth largest closed basin on Earth. The water samples were collected from 51 locations between 2008 and 2009. The inductively coupled plasma‐MS was used for determinations. The obtained U and Zr concentrations are in the range of 37–110 µg L^?1 and 17–78 µg L^?1 in Lake Van and 0.53–0.81 µg L^?1 and 0.15–0.19 µg L^?1 in Lake Hazar, respectively. The concentration of uranium in other studied waters varies from the lowest 0.09 µg L^?1 in Tigris (Dicle) river to the highest 4.0 µg L^?1 in Mediterranean Sea water. Mean Mo and V concentrations in the studied water samples were found to be in ranges of 0.1–17 and 2.7–113 µg L^?1, respectively. The obtained highest U concentration in Lake Van correlates with the highest Mo and Zr levels compared to the Lake Hazar and river waters. These results imply that there is a young occurrence of uranium minerals around Lake Van. It is concluded that there is about 50.000 ton of uranium in Lake Van water.     

Water uptake by trees in a riparian hardwood forest (Rhine floodplain,France)

Water flow in the soil–root–stem system was studied in a flooded riparian hardwood forest in the upper Rhine floodplain. The study was undertaken to identify the vertical distribution of water uptake by trees in a system where the groundwater is at a depth of less than 1 m. The three dominant ligneous species (Quercus robur, Fraxinus excelsior and Populus alba) were investigated for root structure (vertical extension of root systems), leaf and soil water potential (Ψ_m), isotopic signal (¹⁸O) of soil water and xylem sap. The root density of oak and poplar was maximal at a depth of 20 to 60 cm, whereas the roots of the ash explored the surface horizon between 0 and 30 cm, which suggests a complementary tree root distribution in the hardwood forest. The flow density of oak and poplar was much lower than that of the ash. However, in the three cases the depth of soil explored by the roots reached 1·2 m, i.e. just above a bed of gravel. The oak roots had a large lateral distribution up to a distance of 15 m from the trunk. The water potential of the soil measured at 1 m from the trunk showed a zone of strong water potential between 20 and 60 cm deep. The vertical profile of soil water content varied from 0·40 to 0·50 cm³ cm^?3 close to the water table, and 0·20 to 0·30 cm³ cm^?3 in the rooting zone. The isotopic signal of stem water was constant over the whole 24‐h cycle, which suggested that the uptake of water by trees occurred at a relatively constant depth. By comparing the isotopic composition of water between soil and plant, it was concluded that the water uptake occurred at a depth of 20 to 60 cm, which was in good agreement with the root and soil water potential distributions. The riparian forest therefore did not take water directly from the water table but from the unsaturated zone through the effect of capillarity. Copyright © 2007 John Wiley & Sons, Ltd.