Precipitation induced stream flow: An event based chemical and isotopic study of a small stream in the Great Plains region of the USA

A small stream in the Great Plains of USA was sampled to understand the streamflow components following intense precipitation and the influence of water storage structures in the drainage basin. Precipitation, stream, ponds, ground-water and soil moisture were sampled for determination of isotopic (D, ¹⁸O) and chemical (Cl, SO₄) composition before and after two intense rain events. Following the first storm event, flow at the downstream locations was generated primarily through shallow subsurface flow and runoff whereas in the headwaters region – where a pond is located in the stream channel – shallow ground-water and pond outflow contributed to the flow. The distinct isotopic signatures of precipitation and the evaporated pond water allowed separation of the event water from the other sources that contributed to the flow. Similarly, variations in the Cl and SO₄ concentrations helped identify the relative contributions of ground-water and soil moisture to the streamflow. The relationship between deuterium excess and Cl or SO₄ content reveals that the early contributions from a rain event to streamflow depend upon the antecedent climatic conditions and the position along the stream channel within the watershed. The design of this study, in which data from several locations within a watershed were collected, shows that in small streams changes in relative contributions from ground water and soil moisture complicate hydrograph separation, with surface-water bodies providing additional complexity. It also demonstrates the usefulness of combined chemical and isotopic methods in hydrologic investigations, especially the utility of the deuterium excess parameter in quantifying the relative contributions of various source components to the stream flow.     

Quantifying groundwater discharge to a small perennial stream in southern Ontario, Canada

A study of the interaction between groundwater and surface water was undertaken within a small agricultural watershed in southern Ontario, Canada. Groundwater contributions to streamflow were measured along a section of stream during baseflow conditions and during rainfall events. Four techniques were used to estimate the contribution of groundwater to the stream along a 450 m reach (three during baseflow and one during stormflow conditions). Under baseflow conditions, streamflow measurements using the velocity–area technique indicated that the net groundwater flux to the stream during the summer months was 10 ml s⁻¹ m⁻¹. Hydrometric measurements (i.e. hydraulic gradient and hydraulic conductivity) taken using mini-piezometers installed in the sediments beneath the stream resulted in net groundwater flux estimates that were four to five times lower. Seepage meters failed to provide any measurements of water flux into or out of the stream. Therefore, based on these results, the velocity–area technique gives the best estimate of groundwater discharge. Hydrograph separations were conducted using isotopic ratios and electrical conductivity on two large rainfall events with different antecedent moisture conditions in the catchment. Both events showed that pre-event water (generally considered groundwater) dominated streamflow and tile drain flow with 64%–80% of the total discharge contributed by pre-event water. High water table conditions within the catchment resulted in greater stream discharge and a greater contribution of event water in the streamflow than that observed under low water table conditions for similar intensity storm events. The results also showed that differences in riparian zone width, vegetation and surface saturation conditions between the upper and lower catchment can influence the relative magnitude of streamflow response from the two catchment areas.     

Isotope hydrology and water sources in a heavily urbanized stream

Complex networks of both natural and engineered flow paths control the hydrology of streams in major cities through spatio-temporal variations in connection and disconnection of diverse water sources. We used spatially extensive and temporally intensive sampling of water stable isotopes to disentangle the hydrological sources of the heavily urbanized Panke catchment (~220 km²) in the north of Berlin, Germany. The isotopic data enabled us to partition stream water sources across the catchment using a Bayesian mixing analysis. The upper part of the catchment streamflow is dominated by groundwater (~75%) from gravel aquifers. In dry summer periods, streamflow becomes intermittent in the upper catchment, possibly as a result of local groundwater abstractions. Storm drainage dominates the responses to precipitation events. Although such events can dramatically change the isotopic composition of the upper stream network, storm drainage only accounts for 10%–15% of annual streamflow. Moving downstream, subtle changes in sources and isotope signatures occur as catchment characteristics vary and the stream is affected by different tributaries. However, effluents from a wastewater treatment plant (WWTP), serving 700,000 people, dominate stream flow in the lower catchment (~90% of annual runoff) where urbanization effects are more dramatic. The associated increase in sealed surfaces downstream also reduces the relative contribution of groundwater to streamflow. The volume and isotopic composition of storm runoff is again dominated by urban drainage, though in the lower catchment, still only about 10% of annual runoff comes from storm drains. The study shows the potential of stable water isotopes as inexpensive tracers in urban catchments that can provide a more integrated understanding of the complex hydrology of major cities. This offers an important evidence base for guiding the plans to develop and re-develop urban catchments to protect, restore, and enhance their ecological and amenity value.     

Storm-water hydrograph separation of run off from a mine-tailings impoundment formed by thickened tailings discharge at Kidd Creek, Timmins, Ontario

The Kidd Creek Cu---Zn sulphide mine is located near Timmins, Ontario. Mill tailings are thickened and deposited as a thickened slurry in a circular, conical-shaped pile with an area of approximately 1200 ha. Deposition of tailings as a thickened slurry results in a relatively uniform grain-size distribution and hydraulic conductivity, and a thick tension-saturated zone above the water table. The tailings are drained by numerous small, ephemeral stream channels, which have developed in a radial pattern. During storms, water from these streams collects in catchment ponds where it is held before treatment. The contribution of tailings pore water to the run off is of interest because of the potential for discharge of pore water containing high concentrations of Fe(II)-acidity, metals and SO₄ to the stream. Hydraulic head measurements, measurements of water-table elevation and groundwater flow modelling were conducted to determine the mechanisms responsible for tailings pore water entering the surface streams. Chemical hydrograph separation of storm run off in one of these streams, during three rainfall events, using Na and Cl as conservative tracers, indicates that the integrated tailings pore water fraction makes up between less than 1 % and 20% of the total hydrograph. This range is less than the maximum fraction of tailings pore water of 22–65% reported for run off from a conventional tailings deposit. At this site, preferential flow through permeable fractures may be the dominant mechanism causing discharge of tailings pore water to storm run off. Estimates of the mass of Fe(II) that discharges to the surface run off from the pore water range up to 2800 mg s⁻¹ during a moderate intensity, long duration rainfall event. The greatest potential for discharge of significant masses of solutes derived from the pore water exists during long duration rainfall events, when the water table rises to the surface over large areas of the tailings impoundment.     

Groundwater recharge and palaeoclimate in the Sirte and Kufra basins, Libya

Stable and radio-isotope results (C, H, O) for groundwaters from the Sirte and northern Kufra basins are used to determine the recharge history during the Holocene and late Pleistocene. Radiocarbon ages have been corrected on the basis of their stable carbon isotope ratios and on environmental samples from the areas, and two groups may be recognised: (1) low ¹⁴C activity groundwaters (13000–34000 yr. BP) with δ ¹³C-5.6 to −11.7‰; and (2) higher ¹⁴C activity groundwaters (5000–7800 yr. BP) enriched in ¹³C up to δ ¹³C = −3.2‰. There is a general correlation of age with depth.

A well defined freshwater (< 50 mg/l Cl⁻) channel can be traced within the aquifer for some 130 km through the region, which is considered to represent recharge from a former wadi. This water with an age of ± 7800 yr. BP is chemically and isotopically distinct from the regional groundwaters and provides direct evidence of a significant recharge event during the Holocene.

The stable isotope (O and H) composition of groundwater from the Kufra and Sirte basins are all related by an evaporative line with slope δ D = 4.5δ ¹³O − 35 with an intercept on the meteoric line of -11‰. This suggests a recharge source continuing into the Holocene from air masses, analogous to current heavy monsoon rain derived from south of the Sahara. The spatial and temporal distribution of groundwaters in relation to the evaporative line suggests a progressive change in character of the recharge which is controlled by a shift towards strongly convective rainfall during the Holocene.

The direct hydrogeological and geochemical evidence supports climatic models proposed by several workers in which discrete humid episodes during the Holocene are inferred.     

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.     

Contrasts in storm event hydrochemistry in an acidic afforested catchment in upland Wales

The hydrochemistry of stream water in an acidic afforested catchment in the Welsh uplands was monitored routinely between 1985 and 1990. Nineteen storm episodes were sampled intensively during this period. Although the general storm response of the stream can be characterised by increased concentrations of H⁺, Al and dissolved organic carbon (DOC), and a dilution of Ca and SiO₂, the detailed hydrochemistry of individual acid episodes exhibited marked contrasts. The minimum pH reached during specific episodes ranged from 4.1 to 5.0, and peak dissolved Al concentrations varied from 9 to 44 μmol l⁻¹. The reasons for such differences in the hydrochemical response can be identified for each individual episode by examining the complex interactions between (1) the quantity and quality of event precipitation, (2) antecedent patterns of weather and atmospheric deposition and (3) the hydrological processes which dominate the storm runoff response. The dynamic nature of catchment hydrology was found to exert a particularly strong influence on the hydrochemistry of specific acid episodes.     

The role of lower continental crust and lithospheric mantle in the genesis of Plio–Pleistocene volcanic rocks from Sardinia (Italy)

The first comprehensive chemical and Sr–Nd–Pb isotopic data set of Plio–Pleistocene tholeiitic and alkaline volcanic rocks cropping out in Sardinia (Italy) is presented here. These rocks are alkali basalts, hawaiites, basanites, tholeiitic basalts and basaltic andesites, and were divided into two groups with distinct isotopic compositions. The vast majority of lavas have relatively high ⁸⁷Sr/⁸⁶Sr (0.7043–0.7051), low ¹⁴³Nd/¹⁴⁴Nd (0.5124–0.5126), and are characterised by the least radiogenic Pb isotopic composition so far recorded in Italian (and European) Neogene-to-Recent mafic volcanic rocks (²⁰⁶Pb/²⁰⁴Pb=17.55–18.01) (unradiogenic Pb volcanic rocks, UPV); these rocks crop out in central and northern Sardinia. Lavas of more limited areal extent have chemical and Sr–Nd–Pb isotopic ratios indicative of a markedly different source (⁸⁷Sr/⁸⁶Sr=0.7031–0.7040; ¹⁴³Nd/¹⁴⁴Nd=0.5127–0.5129; ²⁰⁶Pb/²⁰⁴Pb=18.8–19.4) (radiogenic Pb volcanic rocks, RPV), and crop out only in the southern part of the island. The isotopic ratios of these latter rocks match the values found in the roughly coeval anorogenic (i.e. not related to recent subduction events in space and time) mafic volcanic rocks of Italy (i.e. Mt. Etna, Hyblean Mts., Pantelleria, Linosa), and Cenozoic European volcanic rocks. The mafic rocks of the two Sardinian rock groups also show distinct trace element contents and ratios (e.g. Ba/Nb>14, Ce/Pb=8–25 and Nb/U=29–38 for the UPV; Ba/Nb<9, Ce/Pb=24–28 and Nb/U=46–54 for the RPV). The sources of the UPV could have been stabilised in the Precambrian after low amounts of lower crustal input (about 3%), or later, during the Hercynian Orogeny, after input of Precambrian lower crust in the source region, whereas the sources of the RPV could be related to processes that occurred in the late Palaeozoic–early Mesozoic, possibly via recycling of proto-Tethys oceanic lithosphere by subduction.     

Improved understanding of spring and stream water responses in headwaters of the Indian Lesser Himalaya using stable isotopes,conductivity and temperature as tracers

Stable isotope data are presented for precipitation, spring and stream water in a headwater catchments in the Indian Lesser Himalaya. Isotopic contents of phreatic groundwater followed the local meteoric water line and showed minimal alteration by evaporation, suggesting fast recharge. Mean isotopic values for springs and the stream were close to the weighted annual mean for precipitation, indicating recharge was in synchrony with seasonal rainfall distribution. Precipitation exhibited isotopic declines of ?0.6‰ and ?0.2‰ δ¹⁸O per 100 m rise in elevation in July and August (monsoon), respectively. The time lag of one month between rainfall and spring discharge, combined with the isotopic lapse rate indicated a recharge elevation of 70–165 m above the spring outflow point, implying the water originated within the catchment. Time series of electrical conductivity and temperature of spring, seepage and stream waters confirmed the rapid recharge and limited storage capacity of the shallow aquifers.     

Isotopic investigation of runoff generation in a glacierized catchment in northern Sweden

In this study, summer rainfall contributions to streamflow were quantified in the sub‐arctic, 30% glacierized Tarfala (21.7 km²) catchment in northern Sweden for two non‐consecutive summer sampling seasons (2004 and 2011). We used two‐component hydrograph separation along with isotope ratios (δ¹⁸O and δD) of rainwater and daily streamwater samplings to estimate relative fraction and uncertainties (because of laboratory instrumentation, temporal variability and spatial gradients) of source water contributions. We hypothesized that the glacier influence on how rainfall becomes runoff is temporally variable and largely dependent on a combination of the timing of decreasing snow cover on glaciers and the relative moisture storage condition within the catchment. The results indicate that the majority of storm runoff was dominated by pre‐event water. However, the average event water contribution during storm events differed slightly between both years with 11% reached in 2004 and 22% in 2011. Event water contributions to runoff generally increased over 2011 the sampling season in both the main stream of Tarfala catchment and in the two pro‐glacial streams that drain Storglaciären (the largest glacier in Tarfala catchment covering 2.9 km²). We credit both the inter‐annual and intra‐annual differences in event water contributions to large rainfall events late in the summer melt season, low glacier snow cover and elevated soil moisture due to large antecedent precipitation. Together amplification of these two mechanisms under a warming climate might influence the timing and magnitude of floods, the sediment budget and nutrient cycling in glacierized catchments. Copyright © 2012 John Wiley & Sons, Ltd.     

“Andesitic water”: a phantom of the isotopic evolution of water-silicate systems. Comment on “Isotopic shifts in waters from geothermal and volcanic systems along convergent plate boundaries and their origin” by W.F. Giggenbach

On account of the low porosity of the lithosphere, intracrustal fluids behave very differently from surface fluids, in that they are changing their geochemical and isotopic labels according to the geological environment. Given a heat source, meteoric waters can be supplied plentifully and their rates of throughput in geothermal systems are sufficiently high to exhaust the compositional signals of a given rock buffer. In contrast, fluids exsolved from magma, and subducted fluids, would be supplied at less than about one tenth of the meteoric rate over the life time of a system. Based on up-to-date flow models, the isotopic evolution of meteoric water interacting with crustal rock follows a curved to L-shaped track in the δD versus δ¹⁸O plot. Instantaneous (present-day) tie-lines between recharge and discharge are secants of such tracks and can have a range of slopes. At the start of an interaction, waters have δD and δ¹⁸O values approaching equilibrium with the original rock composition (water “W1”). Using known hydrogen isotope fractionation factors, W1 values generally plot in the region of “andesite” or “andesitic” waters of various authors. Since the W1 waters have δD values that are on average more positive, and also less variable than those of the meteoric recharges, most tracks and tie-lines have positive slopes, and the plotting of a large number of tie-lines will produce a focus on the field of W1 waters, regardless of the original water source.     

Continuous monitoring of stream δ18O and δ2H and stormflow hydrograph separation using laser spectrometry in an agricultural catchment

A portable Wavelength Scanned‐Cavity Ring‐Down Spectrometer (Picarro L2120) fitted with a diffusion sampler (DS‐CRDS) was used for the first time to continuously measure δ¹⁸O and δ²H of stream water. The experiment took place during a storm event in a wet tropical agricultural catchment in north‐eastern Australia. At a temporal resolution of one minute, the DS‐CRDS measured 2160 δ¹⁸O and δ²H values continuously over a period of 36 h with a precision of ±0.08 and 0.5‰ for δ¹⁸O and δ²H, respectively. Four main advantages in using high temporal resolution stream δ¹⁸O and δ²H data during a storm event are highlighted from this study. First, they enabled us to separate components of the hydrograph, which was not possible using high temporal resolution electrical conductivity data that represented changes in solute transfers during the storm event rather than physical hydrological processes. The results from the hydrograph separation confirm fast groundwater contribution to the stream, with the first 5 h of increases in stream discharge comprising over 70% pre‐event water. Second, the high temporal resolution stream δ¹⁸O and δ²H data allowed us to detect a short‐lived reversal in stream isotopic values (δ¹⁸O increase by 0.4‰ over 9 min), which was observed immediately after the heavy rainfall period. Third, δ¹⁸O values were used to calculate a time lag of 20 min between the physical and chemical stream responses during the storm event. Finally, the hydrograph separation highlights the role of event waters in the runoff transfers of herbicides and nutrients from this heavily cultivated catchment to the Great Barrier Reef. Copyright © 2015 John Wiley & Sons, Ltd.     

Isotope geochemistry of Pantelleria volcanic fluids, Sicily Channel rift: a mantle volatile end-member for volcanism in southern Europe

Chemical and isotopic ratio (He, C, H and O) analysis of hydrothermal manifestations on Pantelleria island, the southernmost active volcano in Italy, provides us with the first data upon mantle degassing through the Sicily Channel rift zone, south of the African–European collision plate boundary. We find that Pantelleria fluids contain a CO₂–He-rich gas component of mantle magmatic derivation which, at shallow depth, variably interacts with a main thermal (100°C) aquifer of mixed marine–meteoric water. The measured ³He/⁴He ratios and δ¹³C of both the free gases (4.5–7.3 R_a and −5.8 to −4.2‰, respectively) and dissolved helium and carbon in waters (1.0–6.3 R_a and −7.1 to −0.9‰), together with their covariation with the He/CO₂ ratio, constrain a ³He/⁴He ratio of 7.3±0.1 R_a and a δ¹³C of ca. −4‰ for the magmatic end-member. These latter are best preserved in fluids emanating inside the active caldera of Pantelleria, in agreement with a higher heat flow across this structure and other indications of an underlying crustal magma reservoir. Outside the caldera, the magmatic component is more affected by air dilution and, at a few sites, by mixing with either organic carbon and/or radiogenic ⁴He leached from the U–Th-rich trachytic host rocks of the aquifer. Pantelleria magmatic end-member is richer in ³He and has a lower (closer to MORB) δ¹³C than all fluids yet analyzed in volcanic regions of Italy and southern Europe, including Mt. Etna in Sicily (6.9±0.2 R_a, δ¹³C=−3±1‰). This observation is consistent with a south to north increasing imprint of subducted crustal material in the products of Italian volcanoes, whose He and C (but also O and Sr) isotopic ratios gradually evolve towards crustal values northward of the African–Eurasian plate collision boundary. Our results for Pantelleria extend this regional isotopic pattern further south and suggest the presence of a slightly most pristine or ‘less contaminated’, ³He-richer mantle source beneath the Sicily Channel rift zone. The lower than MORB ³He/⁴He ratio but higher than MORB CO₂/³He ratio of Pantelleria volatile end-member are compatible with petro-geochemical evidence that this mantle source includes an upwelling HIMU–EM1-type asthenospheric plume component whose origin, according to recent seismic data, may be in the lower mantle.     

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.     

Spatial variation of effective porosity and its implications for discharge in an upland headwater catchment in Scotland

Spatial and temporal measurements of shallow sub-surface soil physical properties were made within a 1 km² upland catchment. The surface soil layer of the catchment was organic rich (>70% organic matter) with a corresponding total porosity of 81%. Monthly point observations of volumetric water content (θ) were combined with point estimates of total porosity () and the porosity <50 μm (_residual), to define the ratio of water filled pore volume:pore volume in pores <50 μm (=θ/_residual). Values of θ/_residual were compared with discharge to test whether mass flow occurred when θ/_residual>1. A correlation between water content and discharge was found, with discharge increasing rapidly when θ/_residual approached unity. Similar relationships between water content and catchment discharge were identified for soil units adjacent to the stream when θ/_residual approached unity. These data suggest that soil pores >50 μm are of crucial importance in determining catchment discharge. Spatial and temporal variations in soil properties related to moisture content of the soil were also observed. Under dry conditions, a clear division based on aspect was noted, the west-facing side of the catchment being wettest. In wetter months, total porosity and soil water content were significantly affected by soil type and the spatial pattern of soil water content was more variable than in the dryer months. The physical quantification of soil properties in the shallow sub-surface layer proved important in explaining different initial changes in discharge from the catchment in response to a rainfall event.     

Isotopic characteristics of precipitation in Slovenia and Croatia: Comparison of continental and maritime stations

The stable isotopic composition of hydrogen and oxygen (δ²H and δ¹⁸O) and tritium activity (³H) were monitored in monthly precipitation at two continental stations (Ljubljana, Zagreb) and six stations along the eastern Adriatic coasts of Slovenia and Croatia in the period 2001–2003. Mean air temperatures and amount of precipitation were also recorded.

Distinct differences in both meteorological and isotopic data between the continental and maritime stations were observed. Seasonal variations in δ¹⁸O are smaller at the maritime stations than at the continental ones due to smaller seasonal temperature variations. A good correlation between δ¹⁸O and δ²H was obtained for each station, and the local meteoric water lines are close to the Global Meteoric Water Line, with a decreasing trend of slope for the south-Adriatic stations. Good correlations between δ¹⁸O in monthly precipitation and mean monthly air temperature were observed at all stations. The slope of δ¹⁸O vs. T varied between 0.37‰ °C⁻¹ and 0.15‰ °C⁻¹. Mean ³H activity and seasonal variation of ³H activity are smaller at maritime stations than at continental ones. Additionally, ³H activity decreases in the NW–SE direction of the Adriatic coast.

The study of spatial variations over this relatively small area rich in geographical and climatic diversities showed the complexity of the isotopic composition of precipitation and the isotopic data obtained for eight stations, most of them in the karstic area along the Adriatic coast, and gave valuable information for regional hydrological investigations and modelling of isotope variability over the Mediterranean basin.     

Role of bedrock groundwater in the rainfall–runoff process in a small headwater catchment underlain by volcanic rock

The role of bedrock groundwater in rainfall–runoff processes is poorly understood. Hydrometric, tracer and subsurface water potential observations were conducted to study the role of bedrock groundwater and subsurface flow in the rainfall–runoff process in a small headwater catchment in Shiranui, Kumamoto prefecture, south‐west Japan. The catchment bedrock consists of a strongly weathered, fractured andesite layer and a relatively fresh continuous layer. Major chemical constituents and stable isotopic ratios of δ¹⁸O and δD were analysed for spring water, rainwater, soil water and bedrock groundwater. Temporal and spatial variation in SiO₂ showed that stream flow under the base flow condition was maintained by bedrock groundwater. Time series of three components of the rainstorm hydrograph (rainwater, soil water and bedrock groundwater) separated by end member mixing analysis showed that each component fluctuated during rainstorm, and their patterns and magnitudes differed between events. During a typical mid‐magnitude storm event, a delayed secondary runoff peak with 1·0 l s⁻¹ was caused by increase in the bedrock groundwater component, whereas during a large rainstorm event the bedrock groundwater component increased to ≈ 2·5 l s⁻¹. This research shows that the contribution of bedrock groundwater and soil water depends strongly on the location of the groundwater table, i.e. whether or not it rises above the soil–bedrock interface. Copyright © 2010 John Wiley & Sons, Ltd.     

Seasonal connections between meteoric water and streamflow generation along a mountain headwater stream

In snowmelt-driven mountain watersheds, the hydrologic connectivity between meteoric waters and stream flow generation varies strongly with the season, reflecting variable connection to soil and groundwater storage within the watershed. This variable connectivity regulates how streamflow generation mechanisms transform the seasonal and elevational variation in oxygen and hydrogen isotopic composition (δ¹⁸O and δD) of meteoric precipitation. Thus, water isotopes in stream flow can signal immediate connectivity or more prolonged mixing, especially in high-relief mountainous catchments. We characterized δ¹⁸O and δD values in stream water along an elevational gradient in a mountain headwater catchment in southwestern Montana. Stream water isotopic compositions related most strongly to elevation between February and March, exhibiting higher δ¹⁸O and δD values with decreasing elevation. These elevational isotopic lapse rates likely reflect increased connection between stream flow and proximal snow-derived water sources heavily subject to elevational isotopic effects. These patterns disappeared during summer sampling, when consistently lower δ¹⁸O and δD values of stream water reflected contributions from snowmelt or colder rainfall, despite much higher δ¹⁸O and δD values expected in warmer seasonal rainfall. The consistently low isotopic values and absence of a trend with elevation during summer suggest lower connectivity between summer precipitation and stream flow generation as a consequence of drier soils and greater transpiration. As further evidence of intermittent seasonal connectivity between the stream and adjacent groundwaters, we observed a late-winter flush of nitrate into the stream at higher elevations, consistent with increased connection to accumulating mineralized nitrogen in riparian wetlands. This pattern was distinct from mid-summer patterns of nitrate loading at lower elevations that suggested heightened human recreational activity along the stream corridor. These observations provide insights linking stream flow generation and seasonal water storage in high elevation mountainous watersheds. Greater understanding of the connections between surface water, soil water and groundwater in these environments will help predict how the quality and quantity of mountain runoff will respond to changing climate and allow better informed water management decisions.     

Metals discharged during different flow conditions from a mixed agricultural‐forest catchment (NW Spain)

Metal loads were determined from water samples collected under different streamflow conditions (baseflow and storm events) in a rural catchment (NW Spain) during 4 years. A study at annual, seasonal and storm‐event scales was carried out. In all analysed scales, the export order was Fe > Al > Mn > Zn > Cu. A high inter‐annual, seasonal and storm‐event scale variability of metal load was observed. The total metal loads in stream were higher during baseflow conditions than during storm events, which only represented 4% of the duration of the study period and 25% of streamflow. During storm events, both Al and Fe loads accounted 45% of the total load of the study period, whereas Mn, Cu and Zn loads represented 42%, 33% and 24%, respectively. This highlights the role of high flows on metal export. Only four big events exported around 30% of load of each metal transported in events. At all time scales, a prevalence of export of particulate metals over dissolved metals was observed, more pronounced for Al, Fe and Mn than for Cu and Zn. The export of metals in the Corbeira catchment is influenced by runoff and, to a lesser extent, by the rainfall amount. Copyright © 2014 John Wiley & Sons, Ltd.     

A comparison of the toluene distillation and vacuum/heat methods for extracting soil water for stable isotopic analysis

Hanford Loam, from Richland, Washington, was used as a test soil to determine the precision, accuracy and nature of two methods to extract soil water for stable isotopic analysis: azeotropic distillation using toluene, and simple heating under vacuum. The soil was oven dried, rehydrated with water of known stable isotopic compositions, and the introduced water was then extracted.

Compared with the introduced water, initial aliquots of evolved water taken during a toluene extraction were as much as 30 ‰ more depleted in D and 2.7 ‰ more depleted in ¹⁸O, whereas final aliquots were as much as 40 ‰ more enriched in D and 14.3 ‰ more enriched in ¹⁸O. Initial aliquots collected during the vacuum/heat extraction were as much as 64 ‰ more depleted in D and 8.4 ‰ more depleted in ¹⁸O than was the introduced water, whereas the final aliquots were as much as 139 ‰ more enriched in D, and 20.8 ‰ more enriched in ¹⁸O. Neither method appears quantitative; however, the difference in stable isotopic composition between the first and last aliquots of water extracted by the toluene method is less than that from the vacuum/heat method. This is attributed to the smaller fractionation factors involved with the higher average temperatures of distillation of the toluene. The average stable isotopic compositions of the extracted water varied from that of the introduced water by up to 1.4 ‰ in δD and 4.2 ‰ in δ¹⁸O with the toluene method, and by 11.0 ‰ in δD and 1.8 ‰ in δ¹⁸O for the vacuum/heat method.

The lack of accuracy of the extraction methods is thought to be due to isotopic fractionation associated with water being weakly bound (not released below 110°C) in the soil. The isotopic effect of this heat-labile water is larger at low water contents (3.6 and 5.2% water by weight) as the water bound in the soil is a commensurately larger fraction of the total. With larger soilwater contents the small volume of water bound with an associated fractionation is not enough to affect the remaining unbound introduced soil water. Pretreatment of the soil to equilibrate the heat-labile water to the test water produced good results for the toluene distillation but not the vacuum/heat extraction method.

Vapors collected over the soils also show stable isotopic variations related to soilwater content. These vapors also appear to be in closer equilibrium with the free water, as extracted by the toluene method, than with the originally introduced water; thus, the soil vapors do not appear to be isotopically affected by the heat-labile water.

The toluene method appears to be better for extracting soil water for stable isotopic analysis because it allows more precise temperature control and excludes the extraction of heat-labile water which is isotopically fractionated. The bound nature of this heat-labile water limits association with the hydrologically active soil water; thus, the exclusion of this water from the soil water attained by toluene distillation may be advantageous. However, the azeotropic nature of toluene distillation affords no benefit and the extraction procedure must continue to completion.