Groundwater and surface water connectivity within the recharge area of Guarani aquifer system during El Niño 2014–2016

Recharge areas of the Guarani Aquifer System (GAS) are particularly sensitive and vulnerable to climate variability; therefore, the understanding of infiltration mechanisms for aquifer recharge and surface run‐off generation represent a relevant issue for water resources management in the southeastern portion of the Brazilian territory, particularly in the Jacaré‐Pepira River watershed. The main purpose of this study is to understand the interactions between precipitation, surface water, and groundwater using stable isotopes during the strong 2014–2016 El Niño Southern Oscillation event. The large variation in the isotopic composition of precipitation (from ?9.26‰ to +0.02‰ for δ¹⁸O and from ?63.3‰ to +17.6‰ for δ²H), mainly associated with regional climatic features, was not reflected in the isotopic composition of surface water (from ?7.84‰ to ?5.83‰ for δ¹⁸O and from ?49.7‰ to +33.6‰ for δ²H), mainly due to the monthly sampling frequency, and groundwater (from ?7.04‰ to ?7.76‰ for δ¹⁸O and from ?49.5‰ to ?44.7‰ for δ²H), which exhibited less variation throughout the year. However, variations in deuterium excess (d‐excess) in groundwater and surface water suggest the occurrence of strong secondary evaporation during the infiltration process, corresponding with groundwater level recovery. Similar isotopic composition in groundwater and surface water, as well as the same temporal variations in d‐excess and line‐conditioned excess denote the strong connectivity between these two reservoirs during baseflow recession periods. Isotopic mass balance modelling and hydrograph separation estimate that the groundwater contribution varied between 70% and 80%, however, during peak flows, the isotopic mass balance tends to overestimate the groundwater contribution when compared with the other hydrograph separation methods. Our findings indicate that the application of isotopic mass balance methods for ungauged rivers draining large groundwater reservoirs, such as the GAS outcrop, could provide a powerful tool for hydrological studies in the future, helping in the identification of flow contributions to river discharge draining these areas.     

Groundwater evolution and mean water age inferred from hydrochemical and isotopic tracers in a tropical confined aquifer

The coastal confined aquifer in the Gulf of Urabá (Colombia) is an important water source for the banana agro‐industry as well as for urban and rural communities. However, the main processes controlling recharge and mixing in the aquifer are still poorly understood. Hydrochemical analyses and stable isotope monitoring were conducted to (a) determine groundwater recharge origin, mean groundwater age, and the main processes governing groundwater chemistry and the potential mixing of marine water and the influence of diffusive processes from the two surrounding aquitard layers. Hydrochemical data indicate that the main processes affecting the dissolved chemical composition include cation exchange, dissolution of carbonated and CO₂, and silicate weathering. δ¹⁸O and δ²H compositions combined with ¹⁴C data highlight the differences in climatic conditions between the recharge zone and the confined section of the aquifer, which is close to the Atlantic Ocean. Groundwater samples with ¹⁴C ages from recent to 28,300 years BP show a depleted isotopic trend ranging from ?6.43‰ to ?9.14‰ in δ¹⁸O and from ?43.2‰ to ?65.7‰ in δ²H. The most depleted δ¹⁸O and δ²H compositions suggest a cooler recharge climate than the current conditions (corresponding to the last glacial period of the late Pleistocene). Depleted δ¹³C values in the total dissolved inorganic carbon indicate the existence of organic material oxidation processes within the geologic formation. These results can be used or transferred to enhance groundwater modelling efforts in other confined coastal aquifers of South America where scarcity of long‐term monitoring data limits water resources planification under a changing climate.     

A Geochemical Approach to Determine Sources and Movement of Saline Groundwater in a Coastal Aquifer

Geochemical evaluation of the sources and movement of saline groundwater in coastal aquifers can aid in the initial mapping of the subsurface when geological information is unavailable. Chloride concentrations of groundwater in a coastal aquifer near San Diego, California, range from about 57 to 39,400 mg/L. On the basis of relative proportions of major‐ions, the chemical composition is classified as Na‐Ca‐Cl‐SO₄, Na‐Cl, or Na‐Ca‐Cl type water. δ²H and δ¹⁸O values range from ?47.7‰ to ?12.8‰ and from ?7.0‰ to ?1.2‰, respectively. The isotopically depleted groundwater occurs in the deeper part of the coastal aquifer, and the isotopically enriched groundwater occurs in zones of sea water intrusion. ⁸⁷Sr/⁸⁶Sr ratios range from about 0.7050 to 0.7090, and differ between shallower and deeper flow paths in the coastal aquifer. ³H and ¹⁴C analyses indicate that most of the groundwater was recharged many thousands of years ago. The analysis of multiple chemical and isotopic tracers indicates that the sources and movement of saline groundwater in the San Diego coastal aquifer are dominated by: (1) recharge of local precipitation in relatively shallow parts of the flow system; (2) regional flow of recharge of higher‐elevation precipitation along deep flow paths that freshen a previously saline aquifer; and (3) intrusion of sea water that entered the aquifer primarily during premodern times. Two northwest‐to‐southeast trending sections show the spatial distribution of the different geochemical groups and suggest the subsurface in the coastal aquifer can be separated into two predominant hydrostratigraphic layers.     

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas,Eastern Kentucky

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ¹³C‐CH₄ and δ²H‐CH₄) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ¹³C‐CH₄ and δ²H‐CH₄ ranged from ?84.0‰ to ?58.3‰ and from ?246.5‰ to ?146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO₂ reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.     

Isotopic and hydrochemistry spatial variation of sulfate for groundwater characterization in karstic aquifers

The Sierra Gorda aquifer is one of the most extensive of southern Spain. The main groundwater discharge is produced at its northern boundary through several high‐flow springs. In this study, stable isotopes of dissolved sulfate (δ³⁴S and δ¹⁸O) and groundwater chemistry were used to determine the origin of the sulfate and to characterize the groundwater flow. We sampled the main springs, as well as other minor outlets related to perched water tables, in order to determine the different sources of SO₄^2? (e.g., dissolution of evaporites and atmospheric deposition). The substantial difference in the amount of dissolved SO₄^2? between the springs located in its northwestern part (≈25 mg/L) and those elsewhere in the northern part (≈60 mg/L) suggests zones with separate groundwater flow systems. A third group of springs, far from the northeastern boundary of the permeable outcrops, shows higher SO₄^2? content than the rest (≈125 mg/L). The isotopic range of sulfate (?0.3‰ to 14.82‰ V‐CTD) points to several sources, including dissolution of Triassic or Miocene evaporites, atmospheric deposition, and decomposition of organic material in the soil. Among these, the dissolution of Triassic gypsum—which overlies the saturated zone as a consequence of the folds and faults that deform the aquifer—is the main source of SO₄^2? (range from 12.79‰ to 14.82‰ V‐CTD). This range is typical for Triassic gypsum. The higher karstification in the western sector, together with important differences in the saturated thickness between the western and eastern sectors, would also be due to the tectonic structure and could explain the difference in SO₄^2? contents in the water. This singular arrangement may cause a higher residence time of groundwater in the eastern sector; thus, a higher contact time with Triassic evaporitic rocks is inferred. Accordingly, the stable isotopes of SO₄^2? are found to be a valuable tool for identifying areas with different flow systems in the saturated zone of karstic aquifers, as well as for evaluating aspects such as the degree of karstification .     

Using stable isotopes of surface water and groundwater to quantify moisture sources across the Yellow River source region

Characterization of stable isotope compositions (δ²H and δ¹⁸O) of surface water and groundwater in a catchment is critical for refining moisture sources and establishing modern isotope–elevation relationships for paleoelevation reconstructions. There is no consensus on the moisture sources of precipitation in the Yellow River source region during summer season. This study presents δ²H and δ¹⁸O data from 111 water samples collected from tributaries, mainstream, lakes, and groundwater across the Yellow River source region during summertime. Measured δ¹⁸O values of the tributaries range from ?13.5‰ to ?5.8‰ with an average of ?11.0‰. Measured δ¹⁸O values of the groundwater samples range from ?12.7‰ to ?10.5‰ with an average of ?11.9‰. The δ¹⁸O data of tributary waters display a northward increase of 1.66‰ per degree latitude. The δ¹⁸O data and d‐excess values imply that moisture sources of the Yellow River source region during summertime are mainly from the mixing of the Indian Summer Monsoon and the Westerlies, local water recycling, and subcloud evaporation. Analysis of tributary δ¹⁸O data from the Yellow River source region and streamwater and precipitation δ¹⁸O data from its surrounding areas leads to a best‐fit second‐order polynomial relationship between δ¹⁸O and elevation over a 4,600 m elevation range. A δ¹⁸O elevation gradient of ?1.6‰/km is also established using these data, and the gradient is in consistence with the δ¹⁸O elevation gradient of north and eastern plateau. Such relationships can be used for paleoelevation reconstructions in the Yellow River source region.     

Origin and Evolution of Aquitard Porewater in the Western Coastal Plain of Bohai Bay,China

High‐salinity paleowater from low‐permeability aquitards in coastal areas can be a major threat to groundwater resources; however, such water has rarely been studied. The chemical and isotopic compositions of porewater extracted from a 200‐m‐thick Quaternary sedimentary sequence in the western coastal plain of Bohai Bay, China, were analyzed to investigate the salinity origin and chemical evolution of porewater in aquitards. Porewater samples derived at depths shallower than 32 m are characterized by Cl‐Na type saline water (total dissolved solids [TDS], 10.9–84.3 g/L), whereas those at depths greater than 32 m comprise Cl·SO₄‐Na type brackish water (TDS, 2.2–6.3 g/L). Saline porewater is interpreted as evaporated seawater prior to halite saturation, as evidenced by Cl‐Br relationships. Although substantial dilution of saline porewater with meteoric water is supported by a wider Cl^? range and δ²H‐δ¹⁸O covariance, the original marine waters were not completely flushed out. The deeper brackish porewater is determined to be a mixture of fresher porewater and brine groundwater and had a component of old brine of less than 10%, as indicated by a mixing model defined using δ²H and Cl^? tracers. Porewater δ²H‐δ¹⁸O relationships and negative deuterium excess ranging from ?25.9‰ to ?2.9‰ indicate the existence of an arid climate since Late Pleistocene in Tianjin Plain. The aquitard porewaters were chemically modified through water‐rock interactions due to the long residence time.     

Water isotopic variability in Mallorca: a path to understanding past changes in hydroclimate

This paper reports the first results on δ¹⁸O and δ²H analysis of precipitations, cave drip waters, and groundwaters from sites in Mallorca (Balearic Islands, western Mediterranean), a key region for paleoclimate studies. Understanding the isotopic variability and the sources of moisture in modern climate systems is required to develop speleothem isotope‐based climate reconstructions. The stable isotopic composition of precipitation was analysed in samples collected between March 2012 and March 2013. The values are in the range reported by GNIP Palma station. Based on these results, the local meteoric water line (LMWL) δ²H = 7.9 (±0.3) δ¹⁸O + 10.8 (±2.5) was derived, with slightly lower slope than Global Meteoric Water Line. The results help tracking two main sources of air masses affecting the study sites: rain events with the highest δ¹⁸O values (> ?5‰) originate over the Mediterranean Sea, whereas the more depleted samples (< ?8‰) are sourced in the North Atlantic region. The back trajectory analysis and deuterium excess values, ranging from 0.4 to 18.4‰, further support our findings. To assess the isotopic variation across the island, water samples from eight caves were collected. The δ¹⁸O values range between ?6.9 and ?1.6‰. With one exception (Artà), the isotopic composition of waters in caves located along the coast (Drac, Vallgornera, Cala Varques, Tancada, and Son Sant Martí) indicates Mediterranean‐sourced moisture masses. By contrast, the drip water δ¹⁸O values for inland caves (Campanet, ses Rates Pinyades) or developed under a thick (>50 m) limestone cap (Artà) exhibit more negative values. A well‐homogenized aquifer supplied by rainwaters of both origins is clearly indicated by groundwater δ¹⁸O values, which show to be within 2.4‰ of the unweighted arithmetic mean of ?7.4‰. Although limited, the isotopic data presented here constitute the baseline for future studies using speleothem δ¹⁸O records for western Mediterranean paleoclimate reconstructions. Copyright © 2016 John Wiley & Sons, Ltd.     

Temporal and spatial variation of water stable isotopes (18O and 2H) in the Kaidu River basin,Northwestern China

Water resources are the most critical factors to ecology and society in arid basins, such as Kaidu River basin. Isotope technique was convenient to trace this process and reveal the influence from the environment. In this paper, we try to investigate the temporal and spatial characteristics in stable isotope (¹⁸O and ²H) of surface water and groundwater in Kaidu River. Through the water stable isotope composition measurement, spatial and temporal characteristics of deuterium (δ²H) and oxygen 18 (δ¹⁸O) were analysed. It is revealed that (1) comparing the stream water line with the groundwater line and local meteorological water line of Urumqi City, it is found that the contribution of precipitation to surface water in stream runoff is the main source, whereas the surface water is the main source of groundwater. Groundwater is mainly drainage of surface runoff in the river; (2) in the main stream of Kaidu River, the spatial variability of river water showed a ‘heavier‐lighter‐heavier’ change along with the main stream for δ¹⁸O, and temporal variability showed higher in summer and lower in winter; (3) the δ¹⁸O and δ²H values of groundwater samples ranged from ?11.36 to ?7.97‰ and ?73.45 to ?60.05‰, respectively. There is an increasing trend of isotopic values along the groundwater flow path. The seasonal fluctuation of δ¹⁸O is not clear in most samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Use of stable isotopes to understand run‐off generation processes in the Red River Delta

This paper presents the use of stable isotopes of water for hydrological characterization and flow component partitioning in the Red River Delta (RRD), the downstream section of the Red River. Water samples were collected monthly during 2015 from the mainstream section of the river and its right bank tributaries flowing through the RRD. In general, δ¹⁸O and δ²H river signatures were depleted in summer–autumn (May–October) and elevated in winter–spring (November–April), displaying seasonal variation in response to regional monsoon air mass contest. The Pacific equatorial–maritime air mass dominates in summer and the northern Asia continental air mass controls in winter. Results show that water of the RRD tributaries stems solely from local sources and is completely separated from water arriving from upstream subbasins. This separation is due to the extensive management of the RRD (e.g., dykes and dams) for the purposes of irrigation and inundation prevention. Mainstream river section δ¹⁸O and δ²H compositions range from ?10.58 and ?73.74‰ to ?6.80 and ?43.40‰, respectively, and the corresponding ranges inside the RRD were from ?9.35 and ?64.27‰ to ?2.09 and ?15.80‰. A combination of data analysis and hydrological simulation confirms the role of upstream hydropower reservoirs in retaining and mixing upstream water. River water inside the RRD experienced strong evaporation characterized by depleted d‐excess values, becoming negative in summer. On the other hand, the main stream of the Red River has d‐excess values around 10‰, indicating moderate evaporation. Hydrograph separation shows that in upstream subbasins, the groundwater fraction dominates the river flow composition, especially during low flow regimes. Inside the RRD, the river receives groundwater during the dry season, whereas groundwater replenishment occurs in the rainy season. Annual evaporation obtained from this hydrograph separation computation was about 6.3% of catchment discharge, the same order as deduced from the difference between subbasin precipitation and discharge values. This study shows the necessity to re‐evaluate empirical approaches in large river hydrology assessment schemes, especially in the context of climate change.     

Stable isotopic and geochemical identification of groundwater evolution and recharge sources in the arid Shule River Basin of Northwestern China

Stable isotopic (δD_VSMOW and δ¹⁸O_VSMOW) and geochemical signatures were employed to constrain the geochemical evolution and sources of groundwater recharge in the arid Shule River Basin, Northwestern China, where extensive groundwater extraction occurs for agricultural and domestic supply. Springs in the mountain front of the Qilian Mountains, the Yumen‐Tashi groundwater (YTG), and the Guazhou groundwater (GZG) were Ca‐HCO₃, Ca‐Mg‐HCO₃‐SO₄ and Na‐Mg‐SO₄‐Cl type waters, respectively. Total dissolved solids (TDS) and major ion (Mg²⁺, Na⁺, Ca²⁺, K⁺, SO₄^2?, Cl^? and NO₃^?) concentrations of groundwater gradually increase from the mountain front to the lower reaches of the Guazhou Basin. Geochemical evolution in groundwater was possibly due to a combination of mineral dissolution, mixing processes and evapotranspiration along groundwater flow paths. The isotopic and geochemical variations in melt water, springs, river water, YTG and GZG, together with the end‐member mixing analysis (EMMA) indicate that the springs in the mountain front mainly originate from precipitation, the infiltration of melt water and river in the upper reaches; the lateral groundwater from the mountain front and river water in the middle reaches are probably effective recharge sources for the YTG, while contribution of precipitation to YTG is extremely limited; the GZG is mainly recharged by lateral groundwater flow from the Yumen‐Tashi Basin and irrigation return flow. The general characteristics of groundwater in the Shule River Basin have been initially identified, and the results should facilitate integrated management of groundwater and surface water resources in the study area. Copyright © 2015 John Wiley & Sons, Ltd.     

Environmental isotopic and hydrochemical characteristics of groundwater systems in Daying and Qicun geothermal fields,Xinzhou Basin,Shanxi, China

The conceptual hydrogeological model of the low to medium temperature Daying and Qicun geothermal fields has been proposed, based on hydrochemical characteristics and isotopic compositions. The two geothermal fields are located in the Xinzhou basin of Shanxi, China and exhibit similarities in their broad‐scale flow patterns. Geothermal water is derived from the regional groundwater flow system of the basin and is characterized by Cl·SO₄‐Na type. Thermal water is hydrochemically distinct from cold groundwater having higher total dissolved solids (TDS) (>0·8 g/l) and Sr contents, but relatively low Ca, Mg and HCO₃ contents. Most shallow groundwater belongs to local flow systems which are subject to evaporation and mixing with irrigation returns. The groundwater residence times estimated by tritium and ¹⁴C activities indicate that deep non‐thermal groundwater (130–160 m) in the Daying region range from modern (post‐1950s) in the piedmont area to more than 9·4 ka BP (Before Present) in the downriver area and imply that this water belong to an intermediate flow system. Thermal water in the two geothermal fields contains no detectable active ¹⁴C, indicating long residence times (>50 ka), consistent with this water being part of a large regional flow system. The mean recharge elevation estimated by using the obtained relationship Altitude (m) = ? 23·8 × δ²H (‰ ) ? 121·3, is 1980 and 1880 m for the Daying and Qicun geothermal fields, respectively. The annual infiltration rates in the Daying and Qicun geothermal fields can be estimated to be 9029 × 10³ and 4107 × 10³ m³/a, respectively. The variable ⁸⁶Sr/⁸⁷Sr values in the thermal and non‐thermal groundwater in the two fields reflect different lithologies encountered along the flow path(s) and possibly different extents of water‐rock interaction. Based on the analysis of groundwater flow systems in the two geothermal fields, hydrogeochemical inverse modelling was performed to indicate the possible water‐rock interaction processes that occur under different scenarios. Copyright © 2010 John Wiley & Sons, Ltd.     

Isotopic Characterization of Sulfate in a Shallow Aquifer Impacted by Agricultural Fertilizer

The stable isotope ratios of groundwater sulfate (³⁴S/³²S, ¹⁸O/¹⁶O) are often used as tracers to help determine the origin of groundwater or groundwater contaminants. In agricultural watersheds, little is known about how the increased use of sulfur as a soil amendment to optimize crop production is affecting the isotopic composition of groundwater sulfate, especially in shallow aquifers. We investigated the isotopic composition of synthetic agricultural fertilizers and groundwater sulfate in an area of intensive agricultural activity, in Ontario, Canada. Groundwater samples from an unconfined surficial sand aquifer (Lake Algonquin Sand Aquifer) were analyzed from multi-level monitoring wells, riverbank seeps, and private domestic wells. Fertilizers used in the area were analyzed for sulfur/sulfate content and stable isotopic composition (δ¹⁸O and/or δ³⁴S). Fertilizers were isotopically distinct from geological sources of groundwater sulfate in the watershed and groundwater sulfate exhibited a wide range of δ³⁴S (−6.9 to +20.0‰) and δ¹⁸O (−5.0 to +13.7‰) values. Quantitative apportionment of sulfate sources based on stable isotope data alone was not possible, largely because two of the potential fertilizer sulfate sources had an isotopic composition on the mixing line between two natural geological sources of sulfate in the aquifer. This study demonstrates that, when sulfate isotope analysis is being used as a tracer or co-tracer of the origin of groundwater or of contaminants in groundwater, sulfate derived from synthetic fertilizer needs to be considered as a potential source, especially when other parameters such as nitrate independently indicate fertilizer impacts to groundwater quality.     

Compound‐Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis‐DCE compound‐specific isotope analysis of carbon and chlorine collected over a 16‐month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis‐DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ³⁷Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis‐DCE. Carbon isotopic values range between ?28.9 and ?20.7‰ VPDB for TCE, and ?26.5 and ?11.8‰ VPDB for cis‐DCE. In most wells, isotopic values remained steady over the 15‐month study. Isotopic enrichment from TCE to cis‐DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine‐carbon isotopic enrichment ratios (?_Cl/?_C) were 0.18 for TCE and 0.69 for cis‐DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume.     

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

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

Spatial and temporal perspectives on spring break‐up flooding in the Slave River Delta,NWT

Spatial and temporal patterns of spring break‐up flooding in the Slave River Delta (SRD), Northwest Territories, are characterized during three years (2003–2005) using water isotope tracers and total inorganic suspended sediment (TSS) concentrations measured from lakewater samples collected shortly after the spring melt. Strongly contrasting spring melt periods led to a moderate flood in 2003, no flooding in 2004 and widespread flooding in 2005. Flooded lakes have isotopically‐depleted δ¹⁸O (δ²H) signatures, ranging between ? 19·2‰ (?145‰) and ? 17·1‰ (?146‰) and most have high TSS concentrations (>10 mg L^?1), while non‐flooded lakes have more isotopically‐enriched δ¹⁸O (δ²H) signatures, ranging between ? 18·2‰ (?149‰) and ? 10·6‰ (?118‰) and low TSS concentrations (<10 mg L^?1). These results, in conjunction with the isotopic signatures of Slave River water and snowmelt, are used to estimate the proportion of river‐ or snowmelt‐induced dilution in delta lakes during the spring of each study year. Calculations indicate river flooding caused dilution of ～70–100% in delta lakes, while snowmelt dilution in the absence of river flooding ranged from ～0–56%. A positive relationship exists between the spatial extent of spring flooding in the SRD and level and discharge on the Slave River and upstream tributaries, suggesting that upstream flow generation plays a key role in determining the magnitude of spring flooding in the SRD. Parallel variations in the 46‐year instrumental Slave River discharge record and flood stratigraphy in the active delta indicate that there is potential for extending the flood history of the SRD, a development that will contribute to a more robust understanding of the drivers of historic, contemporary and future flood frequency in the delta. Copyright © 2008 John Wiley & Sons, Ltd.     

Hydrochemistry of groundwaters in a spa area of Korea: an implication for water quality degradation by intensive pumping

A geochemical study was carried out in a small spa area (Onyang Spa, Korea) where intensive pumping of deep thermal groundwater (1 300 000 m³ year⁻¹) is taking place. This has caused the deep fractures to lose their artesian pressure and the upper shallow fractures have been encroached by shallow, cold waters. To quantify the influence of long‐term heavy pumping on the quality of the geothermal water, groundwater sampling and chemical analysis, water‐level measurement, and well loggings were performed for the selected deep thermal wells and shallow cold wells. Chemical analysis results indicate a big contrast in water chemistry and origins between the two water types. Shallow groundwater shows a wider concentration ranges in solutes that are closely related to human activity, illustrating the water's vulnerability to contamination near the land surface. Plots of water chemistry as a function of fluoride reveal that the quality of the thermal water was greatly influenced by the shallow, cold groundwater and that intensive pumping of the deep thermal groundwater has caused the introduction of shallow groundwater into the deeper fractures. Although the deep and the shallow fractures were piezometrically separated to some extent, a mixing model based on fluoride and nitrate indicated that the cold‐water fractions in the thermal wells are up to 50%. This suggests that the thermal water is faced with water quality degradation by the downward flow of the shallow, cold water. Restriction on the total of all the pumpage permits per unit area is suggested to restore the artesian pressure of the deep thermal aquifer and to prevent cold‐water intrusion in the study area. Copyright © 2004 John Wiley & Sons, Ltd.     

Major active faults determine the location of the Tongonan geothermal field: Evidence provided by rock alteration and stable isotope geochemistry

Abstract The influence of major active faults on rock alteration and stable isotope geochemistry is described for the Tongonan geothermal field, Leyte, the Philippines. In the Pliocene, acid alteration with characteristic iron enrichment (3 g/100 g) and calcium depletion (2 g/100 g) occurred along a Riedel shear fault in the Malitbog sector, and initial minor acid alteration also occurred along a similar shear in the Mahiao sector. Later, sodium metasomatism (5 g/100 g) coincided with the highest aquifer chloride (10 000 mg/kg) as a result of dissociation of saline magmatic fluids discharging through the reservoir rocks in the Upper Mahiao. The incursion of magmatic fluids (possibly δD 35‰, δ¹⁸O +7‰) set up a vigorous convection cell of meteoric water, which focused around low‐angle (L) shears centered in the Sambaloran sector. Meteoric water (δD ?35 to ?40‰, δ¹⁸O ?6 ± 1‰) depleted the reservoir in silica (6 g/100 g) and potassium (1–2 g/100 g). It also completely exchanged oxygen isotopes rapidly (within months) at high temperatures (300–400°C), and now does so continuously with fractured isotopically fresh or incompletely altered rock at small scales (centimeters or less) exposed by a 2 cm/year creep around the L shears to form a new component called geothermal water. Geothermal water mixes with meteoric water at lower temperatures (<300°C) to create the characteristic shift in δ¹⁸O of 6‰ at near constant δD (?35 ± 5‰). The 10‰ variation in δD is due to groundwater recharge derived from rain falling on steep terrain (5‰) and to enrichment of deuterium in boiling saline solutions (5‰); it is not due to two‐component mixing of meteoric with magmatic water. The low (～1) isotopic water/rock (W/R) ratios calculated from oxygen isotopes in previously published reports are meaningless, because the water contains four components (predominantly geothermal and meteoric water; <10% magmatic and rock water). W/R ratios of up to 1500 calculated from spring and rock chemistry are more realistic and, with a flow rate of approximately 50 L/s through a 30 km³ reservoir, can account for the estimated 3 My age of the system.     

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.     

Isotope hydrology of the Allt a' Mharcaidh catchment,Cairngorms, Scotland: implications for hydrological pathways and residence times

The hydrology of oxygen‐18 (¹⁸O) isotopes was monitored between 1995 and 1998 in the Allt a' Mharcaidh catchment in the Cairngorm Mountains, Scotland. Precipitation (mean δ¹⁸O=−7·69‰) exhibited strong seasonal variation in δ¹⁸O values over the study period, ranging from −2·47‰ in the summer to −20·93‰ in the winter months. As expected, such variation was substantially damped in stream waters, which had a mean and range of δ¹⁸O of −9·56‰ and −8·45 to −10·44‰, respectively. Despite this, oxygen‐18 proved a useful tracer and streamwater δ¹⁸O variations could be explained in terms of a two‐component mixing model, involving a seasonally variable δ¹⁸O signature in storm runoff, mixing with groundwater characterized by relatively stable δ¹⁸O levels. Variations in soil water δ¹⁸O implied the routing of depleted spring snowmelt and enriched summer rainfall into streamwaters, probably by near‐surface hydrological pathways in peaty soils. The relatively stable isotope composition of baseflows is consistent with effective mixing processes in shallow aquifers at the catchment scale. Examination of the seasonal variation in δ¹⁸O levels in various catchment waters provided a first approximation of mean residence times in the major hydrological stores. Preliminary estimates are 0·2–0·8 years for near‐surface soil water that contributes to storm runoff and 2 and >5 years for shallow and deeper groundwater, respectively. These ¹⁸O data sets provide further evidence that the influence of groundwater on the hydrology and hydrochemistry of upland catchments has been underestimated. Copyright © 2000 John Wiley & Sons, Ltd.