Search

The use of the annual cycles of stable isotopes to estimate the parameters of transit time distribution (TTD) functions has been recently criticized by Kirchner who showed that if the catchment is heterogeneous the mean residence time calculated from the damping of the amplitude of the input signal is often underestimated by large factors. We modify Kirchner's initial analysis and show that the estimation bias is a function of the degree of heterogeneity. In low heterogeneity cases corresponding to permeable aquifers, the TTD of a simple exponential model developed assuming a homogeneous medium deviates only slightly from the true TTD, and thus estimated and true mean transit times are close. We also develop and test for a sandstone aquifer a model predicting the temperature amplitude of water at the outlet of a groundwater system from the annual air temperature cycle, and show that even though temperature is not a conservative tracer, it can be used to calibrate a lumped parameter model describing the TTD of the aquifer.

Environmental isotopes and hydrogeological data have been used for the construction of a conceptual model of fresh groundwater flow in the Klodzko Basin, Sudetes, Poland. The model has allowed the verification of a groundwater circulation scheme resulting from the general morphological assumptions and the recharge role to the surrounding mountains. Combined interpretation of the tritium ages and the isotopic altitude effect allowed determining the volume of water-bearing rock Vr and hydrogeological parameters of systems drained by springs and wells. Prior to the final determination of the recharge zone of individual objects, calculations were made for the thickness of the flow zone (h) and the distance from the recharge zone to the drainage point (L). The recharge areas for springs are located within a distance of 1–1.5 km and are characterized by a width of 0.75–1.65 km. The recharge area of wells is located in significantly longer distances of 2.1–12 km but yet definitely lower width. The rechar...

The use of the annual cycles of stable isotopes to estimate the parameters of transit time distribution functions has been recently criticised by Kirchner (2016). The author shows that the mean residence time of heterogeneous catchments calculated from the damping of the amplitude of the input signal are very often over-estimates, sometimes by large factors. We show here that the overestimation depends on the relative time scales of the cycle’s frequency and the mean transit time and that tracer cycles can still be used, at least for groundwater systems sustained by baseflow. Firstly it appears that an exponential model is a good approximation for the transit time distribution of a heterogeneous groundwatershed if the subgroundwatersheds’ transit time distributions are themselves exponential and their mean transit times are in the same range or slightly higher than the period of the tracer cycle. Secondly, we suggest that tracer cycles can still be used as secondary data to test whether the degree of heterogeneity of the subsurface is small enough to warrant approximating it by a homogeneous medium. Lastly, we develop a model predicting the amplitude of groundwater temperature from the annual air temperature cycle, and show that even though temperature is not a conservative tracer, it can be useful for groundwater dating. The potential use of the temperature cycle is illustrated in the case-study of a sandstone aquifer drained by contact springs.

Douala city, located in the littoral province of Cameroon, receives abundant rainfall quantities due to its geographical position in the Gulf of Guinea and bears considerable surface water and groundwater resources. Due to socioeconomic development and rapid demographic growth in the city and its consequences of unplanned urbanization and improper sanitation system, these water resources are poorly protected and managed. Streams in the Wouri watershed receive large amounts of wastewater discharge, and hundreds of boreholes have been drilled into the aquifer system without any management plan. A detailed hydrodynamic and hydrogeochemistry study in Douala town and its environs was conducted to get a better insight into the groundwater system functioning in order to provide information for the sustainable management and protection of the groundwater resource. Two field campaigns were carried out with 187 samples collected and analyzed for major ions, stable isotopes (18O, 2H), and tritium 3H. The results of the sampling have shown that the weathering of silicate minerals is the dominant geochemical process affecting groundwater chemistry in this system. However, acid rainfall in the humid climate has also caused carbonate mineral dissolution, amorphous silica deposition, and ion exchange reactions to occur in aquifers in the region. The various water types identified were categorized into four major clusters C1 to C4, based on the major ion composition and the local hydrogeological conditions. Environmental isotope data reveal that modern-to-submodern waters occur in the phreatic Quaternary/Mio-Pliocene and Oligocene/Upper Eocene aquifers, respectively. These results corroborate with the conceptual model built where modern groundwater types indicated silicate mineral weathering and calcite dissolution (C1 and C2), whereas submodern groundwater mostly showed silica deposition, ion exchange, and, to a lesser extent, carbonate mineral dissolution (C3 and C4). This improved understanding of the aquifer system functioning is essential to provide a reasonable basis for effective control measures and sustainable water management.

Diffusive mass exchange into immobile water regions within heterogeneous porous aquifers influences the fate of solutes. The percentage of immobile water is often unidentified in natural aquifers though. Hence, the mathematical prediction of solute transport in such heterogeneous aquifers remains challenging. The objective of this study was to find a simple analytical model approach that allows quantifying properties of mobile and immobile water regions and the portion of immobile water in a porous system. Therefore, the Single Fissure Dispersion Model (SFDM), which takes into account diffusive mass exchange between mobile and immobile water zones, was applied to model transport in well-defined saturated dual-porosity column experiments. Direct and indirect model validation was performed by running experiments at different flow velocities and using conservative tracer with different molecular diffusion coefficients. In another column setup, immobile water regions were randomly distributed to test the model applicability and to determine the portion of immobile water. In all setups, the tracer concentration curves showed differences in normalized maximum peak concentration, tailing and mass recovery according to their diffusion coefficients. These findings were more pronounced at lower flow rates (larger flow times) indicating the dependency of diffusive mass exchange into immobile water regions on tracers' molecular diffusion coefficients. The SFDM simulated all data with high model efficiency. Successful model validation supported the physical meaning of fitted model parameters. This study showed that the SFDM, developed for fissured aquifers, is applicable in porous media and can be used to determine porosity and volume of regions with immobile water. Copyright © 2015 John Wiley & Sons, Ltd.

In recent years, constructed wetland systems have become into focus as means of cost-efficient organic contaminant management. Wetland systems provide a highly reactive environment in which several removal pathways of organic chemicals may be present at the same time; however, specific elimination processes and hydraulic conditions are usually separately investigated and thus not fully understood. The flow system in a three dimensional pilot-scale horizontal subsurface constructed wetland was investigated applying a multi-tracer test combined with a mathematical model to evaluate the flow and transport processes. The results indicate the existence of a multiple flow system with two distinct flow paths through the gravel bed and a preferential flow at the bottom transporting 68% of tracer mass resulting from the inflow design of the model wetland system. There the removal of main contaminant chlorobenzene was up to 52% based on different calculation approaches. Determined retention times in the range of 22d to 32.5d the wetland has a heterogeneous flow pattern. Differences between simulated and measured tracer concentrations in the upper sediment indicate diffusion dominated processes due to stagnant water zones. The tracer study combining experimental evaluation with mathematical modeling demonstrated the complexity of flow and transport processes in the constructed wetlands which need to be taken into account during interpretation of the determining attenuation processes.

Microbial communities are the driving force behind the degradation of contaminants like aromatic hydrocarbons in groundwater ecosystems. However, little is known about the response of native microbial communities to contamination in pristine environments as well as their potential to recover from a contamination event. Here, we used an indoor aquifer mesocosm filled with sandy quaternary calciferous sediment that was continuously fed with pristine groundwater to study the response, resistance and resilience of microbial communities to toluene contamination over a period of almost two years, comprising 132 days of toluene exposure followed by nearly 600 days of recovery. We observed an unexpectedly high intrinsic potential for toluene degradation, starting within the first two weeks after the first exposure. The contamination led to a shift from oxic to anoxic, primarily nitrate-reducing conditions as well as marked cell growth inside the contaminant plume. Depth-resolved community fingerprinting revealed a low resistance of the native microbial community to the perturbation induced by the exposure to toluene. Distinct populations that were dominated by a small number of operational taxonomic units (OTUs) rapidly emerged inside the plume and at the plume fringes, partially replacing the original community. During the recovery period physico-chemical conditions were restored to the pristine state within about 35 days, whereas the recovery of the biological parameters was much slower and the community composition inside the former plume area had not recovered to the original state by the end of the experiment. These results demonstrate the low resilience of sediment-associated groundwater microbial communities to organic pollution and underline that recovery of groundwater ecosystems cannot be assessed solely by physico-chemical parameters.

A structure model was used to analyse solute-transport parameter estimates based on tracer breakthrough curves. In the model system, groundwater flow is envisioned to be organised in a complex conduit network providing a variety of short circuits with relative small carrying capacities along different erosion levels. The discharge through the fully filled conduits is limited owing to void geometries and turbulent flow; thus, a hierarchic overflow system evolves where conduits are (re-)activated or dried up depending on the flow condition. Exemplified on the Lurbach–Tanneben karst aquifer, the applicability of the model approach was tested. Information derived from multi-tracer experiments performed at different volumetric flow rates enabled to develop a structural model of the karst network, under constraint of the geomorphological and hydrological evolution of the site. Depending on the flow rate, groundwater is divided into up to eight flow paths. The spatial hierarchy of flow paths controls the sequence of flow path activation. Conduits of the topmost level are strongly influenced by reversible alteration processes. Sedimentation or blocking causes an overflow of water to the next higher conduit. Flow path specific dissolutional denudation rates were estimated using the temporal development of the partial discharge. Copyright © 2012 John Wiley & Sons, Ltd.

Regional degradation of groundwater resources by nitrate has become one of the main challenges for water managers worldwide. Regulations have been defined to reverse observed nitrate trends in groundwater bodies, such as the Water Framework Directive and the Groundwater Daughter Directive in the European Union. In such a context, one of the main challenges remains to develop efficient approaches for groundwater quality assessment at regional scale, including quantitative numerical modelling, as a decision support for groundwater management. A new approach combining the use of environmental tracers and the innovative ‘Hybrid Finite Element Mixing Cell’ (HFEMC) modelling technique is developed to study and forecast the groundwater quality at the regional scale, with an application to a regional chalk aquifer in the Geer basin in Belgium. Tritium data and nitrate time series are used to produce a conceptual model for regional groundwater flow and contaminant transport in the combined unsaturated and saturated zones of the chalk aquifer. This shows that the spatial distribution of the contamination in the Geer basin is essentially linked to the hydrodynamic conditions prevailing in the basin, more precisely to groundwater age and mixing and not to the spatial patterns of land use or local hydrodispersive processes. A three-dimensional regional scale groundwater flow and solute transport model is developed. It is able to reproduce the spatial patterns of tritium and nitrate and the observed nitrate trends in the chalk aquifer and it is used to predict the evolution of nitrate concentrations in the basin. The modelling application shows that the global inertia of groundwater quality is strong in the basin and trend reversal is not expected to occur before the 2015 deadline fixed by the European Water Framework Directive. The expected time required for trend reversal ranges between 5 and more than 50 years, depending on the location in the basin and the expected reduction in nitrate application. To reach a good chemical status, nitrate concentrations in the infiltrating water should be reduced as soon as possible below 50 mg/l; however, even in that case, more than 50 years is needed to fully reverse upward trends.

The occurrence of two pharmaceuticals, ibuprofen and diclofenac, in a vulnerable karst groundwater system was investigated. The hydrogeology of the karst system was identified by collecting (3)H samples in groundwater over 27years and by performing tracer tests. The isotopes and tracer data were interpreted by mathematical modeling to estimate the mean transit time of water and to characterize the hydrogeological flow paths in the groundwater system. By this approach, a mean (3)H transit time of 4.6 years for the fissured-porous karst aquifer was determined, whereas the fast flowing water in the conduit system showed a mean transit time of days. Both pharmaceuticals which infiltrated along sinkholes and small streams into the karst system were detected in concentrations of up to approximately 1 microg/L in effluent water of the wastewater treatment plants. Diclofenac was present in most samples collected from four springs discharging the karst groundwater to the rivers Altmühl and Anlauter in concentrations between 3.6 and 15.4 ng/L. In contrast, ibuprofen was rarely detected in groundwater. The results of this study suggest that both pharmaceuticals move into the fractured system of the karst system and go into storage. Thus dilution processes are the dominant control on the concentrations of both pharmaceuticals in the fractured system, whereas biodegradation is likely less important.

Groundwater and surface water samples were collected to improve understanding of the Senegal River Lower Valley and Delta system, which is prone to salinization. Inorganic ion concentrations and environmental isotopes (18O, 2H and 3H) in groundwater, river, lake and precipitation were investigated to gain insight into the functioning of the system with regard to recharge sources and process, groundwater renewability, hydraulic interconnection and geochemical evolution. The geochemical characteristics of the system display mainly cation (Ca2+ and/or Na+) bicarbonated waters, which evolve to chloride water type; this occurs during groundwater flow in the less mineralized part of the aquifer. In contrast, saline intrusion and secondary brines together with halite dissolution are likely to contaminate the groundwater to Na–Cl type. Halite, gypsum and calcite dissolution determine the major ion (Na+, Cl−, Ca2+, Mg2+, SO42− and HCO3−) chemistry, but other processes such as evaporation, salt deposition, ion exchange and reverse exchange reactions also control the groundwater chemistry. Both surface water and groundwater in the system show an evaporation effect, but high evaporated signatures in the groundwater may be due to direct evaporation from the ground, infiltration of evaporated water or enriched rainwater in this region. The stable isotopes also reveal two types of groundwater in this system, which geomorphologically are distributed in the sand dunes (depleted isotopes) and in the flood plain (enriched isotopes). Consideration of the 3H content reinforces this grouping and suggests two mechanisms of recharge: contribution of enriched surface water in recharging the flood plain groundwater and, in the sand dunes area where water table is at depth between 8 and 13 m, slow recharge process characterized the submodern to mixed water.

Summary The mean transit time of groundwater is commonly expected to increase gradually with increasing depth below water table. The present study provides evidence that the theoretical distribution of transit times may be significantly altered depending on the thickness of the unsaturated zone. An unconfined porous groundwater system formed by Tertiary sediments (Test Field Scheyern close to Munich in southern Germany) is overlain by an unsaturated zone with variable thickness between 4 and 60 m. Between 1992 and 2007 the groundwater system has been repeatedly sampled for tritium contents at different depths using two high-resolved wells. Modelled tritium concentrations by using a lumped parameter approach yielded depth profiles of mean transit times of tracer. In one well the profile was characterized by two local transit time maxima, each of approximately 100 years. A moving particle approach (MPA) developed in this study was used on the streamlines between the recharge zones linked to different sampling depths in the well. This suggested that the observed transit time in the profile was mainly governed by variable travel distances of the tracer through the unsaturated zone at the points of recharge. This finding was confirmed at a second multi-level well of the test site. The lumped parameter modelling of chlorofluorocarbon data yielded lower transit times as compared to those obtained from tritium data. This effect was explained by the different behaviour of tritium and chlorofluorocarbons in the unsaturated zone. The study clearly shows that the impact of a variable thickness of the unsaturated zone may overweigh the effect of local heterogeneities. Such transit time distributions of water in porous aquifers as observed in the present study can only be achieved with the help of environmental tracer data.

Summary 3 H, δ 18 O and δ 2 H measurements on groundwater and chemical and isotope analyses on groundwater sulfate were used to determine the origin and mean transit times of groundwater and the sources affecting groundwater sulfate in a high-alpine karstic catchment area in southern Germany. Modelling results using a lumped parameter approach yielded mean transit times of water between 4 and 12 years for different karst springs. However, results obtained from δ 18 O and δ 2 H measurements on groundwater showed that a calculated mean transit time of 12 years for groundwater flow in one karst system can only be explained by mixing of young and old tritium-free ice and snowmelt water. Groundwater sulfate characterized by δ 34 S values of around 20‰ and δ 18 O values of ca. 12‰ in concert with sulfate concentrations of approximately 11 mg/L are probably affected by evaporites. In contrast, δ 34 S values of around 6‰ and δ 18 O values up to 9.4‰ in concert with sulfate concentrations between 1 and 7 mg/L mainly derive from atmospheric deposition. However, a δ 34 S value of −7.3‰ identified for one of the karst springs demonstrates that the oxidation of sulfide-containing minerals must be considered as an additional source, affecting sulfate concentrations in groundwater. The estimated transit time distribution of groundwater shows relatively high mean transit times between 2 and 5 years with a low contribution of very short transit times of less than 1 year. The high contribution of long mean transit times of groundwater in the alpine karst system, which represents an important drinking water resource, is an important function for drinking water supplies.

Summary Lake–ground water interactions in the vicinity of a dredge lake (Lake Leis; SW Germany) were studied by means of the stable isotopes ( 18 O, 2 H) mainly to determine the capture zone of a pumping well for the drinking water supply to the nearby town of Baden-Baden. The water supply is situated in a Quaternary gravel aquifer of the Rhine Valley. Numerical simulation performed using a two-dimensional water flow model was not able to characterise the capture zone uniquely. Several best fit options were possible by applying the values of hydraulic conductivities obtained from the pumping tests. As a result it was not possible to define whether Lake Leis is situated either completely inside or fully outside of the capture zone. To overcome this problem and to define the shape of the catchment area of the water supply precisely, a two-dimensional water flow and tracer transport model was established using both hydraulic heads and isotope data. The isotope data were applied to determine the proportion of lake water in down-gradient pumping and observation wells. Additionally, the isotope compositions of lake water and those in observation wells, measured as a function of time, were used to determine the mean water velocity ( v = 0.6 m/d) along some selected 200 m long flow-paths. Based on known porosity and hydraulic gradient values, a hydraulic conductivity of about k = 6 × 10 −4 m/s was determined for the central area down-gradient of the lake. This hydraulic conductivity and the proportion of lake water in the groundwater were used to calibrate a numerical two-dimensional regional scale transport model. The study demonstrates that it is possible to calibrate a water flow model in the vicinity of a dredge lake uniquely, only when stable isotope signals measured in a time series in both the lake and groundwater are taken into consideration. The calibrated model finally enables the capture zone of the production well to be precisely defined.

Denitrification is an important natural attenuation process that has been observed in many fissured and porous aquifers. However, an important factor limiting denitrification in aquatic systems is the microbial availability of electron donors. Pyrite as the most abundant sulfide mineral in nature represents one of the potential electron sources for denitrifiers to reduce nitrate, but the reaction mechanisms coupling denitrification processes to pyrite oxidation are still questionable. We utilized hydrochemical data and stable isotopes of nitrate and sulfate in groundwater, isotope ratios of sulfur compounds in aquifer sediments and tritium based groundwater dating for assessing denitrification processes in a pyrite-bearing porous groundwater system. The oxic part of the aquifer with mean water transit times of approximately 60 years was characterized by nitrate concentrations of around 15 mg/l and δ 15 N values were similar to those typical for nitrification. In contrast, in the anoxic part with mean water transit times of up to 100 years, low nitrate concentrations accompanied by elevated δ 15 N values were observed. Furthermore, isotope data of groundwater sulfate and sulfur compounds in the aquifer sediment suggest that pyrite oxidation is the dominant source of sulfate in the aquifer. The trend of increasing δ 15 N values and decreasing nitrate concentrations in concert with depleted δ 34 S values of groundwater sulfate similar to δ 34 S values of pyrite, FeS 2 , suggests that denitrification is coupled to pyrite oxidation, particularly when water mean transit time is elevated.

Summary Combined use of tracers and mathematical modelling for evaluation of hydraulic characteristics of constructed wetlands is presented for the subsurface-flow system with Phrag- mites australis in Nowa Supia (Poland). Instantaneously injected bromide and tritium tracers were used to obtain residence time distributions of wastewaters in three parallel inhomoge- neous gravel cells of the wetland. The multi flow dispersion model, which assumes the exis- tence of several flow-paths with different hydraulic properties was developed using the respective parallel combination of analytical solutions of the one-dimensional advection-dis- persion equation. The model was used successfully to fit the experimental tracer breakthrough curves. Different flow components were identified and wastewater volumes, water-saturated porosity, mean wastewater travel times, longitudinal dispersivities as well as hydraulic conduc- tivity of wetland cells were derived from model parameters. The variation in flow components and apparent hydraulic characteristics among wetland cells relate to the improper design and maintenance of the wetland. The single fissure dispersion model, which assumes possible diffu- sion of tracers into the zones with stagnant water during convective-dispersive flow through the mobile zone is adopted to the research conditions and used to model the TBC-s for one cell. The results show that this model can be calibrated with the satisfactory accuracy in that cell but yields unacceptable values of some parameters.

Compound-specific stable isotope analysis (CSIA) is one of the most important methods for assessing biodegradation activities in contaminated aquifers. Although the concept is straightforward, the proof that the method cannot be only used for a qualitative analysis but also to quantify biodegradation in the subsurface was missing. We therefore performed a multitracer test in the field with ring-deuterated (d5) and completely (d8) deuterium-labeled toluene isotopologues (400 g) as reactive tracers as well as bromide as a conservative tracer. The compounds were injected into the anoxic zone of a BTEX plume located down-gradient of the contaminant source. Over a period of 4.5 months the tracer concentrations were analyzed at two control planes located 24 and 35 m downgradient of the injection well. Deuterium-labeled benzylsuccinate was found in the aquifer, indicating the anaerobic biodegradation of deuterated toluene via the benzylsuccinate synthase pathway. Three independent methods were applied to quantify biodegradation of deuterated toluene. First, fractionation of toluene-d8 and toluene-d5 using the Rayleigh equation and an appropriate laboratory-derived isotope fractionation factor was used for the calculation of the microbial decomposition of deuterated toluene isotopologues (CSIA-method). Second, the biodegradation was quantified by the changes of the concentrations of deuterated toluene relative to bromide. Both methods gave similar results, implying that the CSIA-method is a reliable tool to quantify biodegradation in contaminated aquifers. The results of both methods yielded a biodegradation of deuterated toluene isotopologues of approximately 23-29% for the first and 44-51% for the second control plane. Third, the mineralization of deuterated toluene isotopologues was verified by determination of the enrichment of deuterium in the groundwater. This method indicated that parts of deuterium were assimilated into the biomass of toluene degrading microorganisms.

The hydrochemistry of minor elements bromide (Br), boron (B), strontium (Sr), environmental stable isotopes (18O and 2H) together with major-ion chemistry (chloride, sodium, calcium) has been used to constrain the source(s), relative age, and processes of salinization in the Continental Terminal (CT) aquifer in the Saloum (mid-west Senegal) region. Seventy-one groundwater wells which include 24 wells contaminated by saltwater and three sites along the hypersaline Saloum River were sampled to obtain additional information on the hydrochemical characteristics of the groundwater defined in previous studies. Use of Br against Cl confirms the Saloum River saline water intrusion up to a contribution of 7% into the aquifer. In addition to this recent intrusion, a relatively ancient intrusion of the Saloum River water which had reached at least as far as 20 km south from the source was evidenced. The high molar ratio values of Sr/Cl and Sr/Ca indicate an additional input of strontium presumably derived from carbonate precipitation/dissolution reactions and also via adsorption reactions. The variable B concentrations (7-650 microg/L) found in the groundwater samples were tested against the binary mixing model to evaluate the processes of salinization which are responsible for the investigated system. Sorption of B and depletion of Na occur as the Saloum river water intrudes the aquifer (salinization) in the northern part of the region, whereas B desorption and Na enrichment occur as the fresh groundwater flushing displaces the saline waters in the coastal strip (refreshening). In the central zone where ancient intrusion prevailed, the process of freshening of the saline groundwater is indicated by the changes in major-ion chemistry as well as B desorption and Na enrichment. In addition to these processes, stable isotopes reveal that mixing with recently infiltrating waters and evaporation contribute to the changes in isotopic signature.

A confined aquifer in the Malm Karst of the Franconian Alb, South Germany was investigated in order to understand the role of the vadose zone in denitrifiaction processes. The concentrations of chemical tracers Sr2+ and Cl− and concentrations of stable isotope 18O were measured in spring water and precipitation during storm events. Based on these measurements a conceptual model for runoff was constructed. The results indicate that pre-event water, already stored in the system at the beginning of the event, flows downslope on vertical and lateral preferential flow paths. Chemical tracers used in a mixing model for hydrograph separation have shown that the pre-event water contribution is up to 30%. Applying this information to a conceptual runoff generation model, the values of δ15N and δ18O in nitrate could be calculated. Field observations showed the occurence of significant microbial denitrification processes above the soil/bedrock interface before nitrate percolates through to the deeper horizon of the vadose zone. The source of nitrate could be determined and denitrification processes were calculated. Assuming that the nitrate reduction follows a Rayleigh process one could approximate a nitrate input concentration of about 170 mg/l and a residual nitrate concentration of only about 15%. The results of the chemical and isotopic tracers postulate fertilizers as nitrate source with some influence of atmospheric nitrate. The combined application of hydrograph separation and determination of isotope values in δ15N and δ18O of nitrate lead to an improved understanding of microbial processes (nitrification, denitrification) in dynamic systems.

Lumped-parameter models are commonly applied for determining the age of water from time records of transient environmental tracers. The simplest models (e.g. piston flow or exponential) are also applicable for dating based on the decay or accumulation of tracers in groundwater systems. The models are based on the assumption that the transit time distribution function (exit age distribution function) of the tracer particles in the investigated system adequately represents the distribution of flow lines and is described by a simple function. A chosen or fitted function (called the response function) describes the transit time distribution of a tracer which would be observed at the output (discharge area, spring, stream, or pumping wells) in the case of an instantaneous injection at the entrance (recharge area). Due to large space and time scales, response functions are not measurable in groundwater systems, therefore, functions known from other fields of science, mainly from chemical engineering, are usually used. The type of response function and the values of its parameters define the lumped-parameter model of a system. The main parameter is the mean transit time of tracer through the system, which under favourable conditions may represent the mean age of mobile water. The parameters of the model are found by fitting calculated concentrations to the experimental records of concentrations measured at the outlet. The mean transit time of tracer (often called the tracer age), whether equal to the mean age of water or not, serves in adequate combinations with other data for determining other useful parameters, e.g. the recharge rate or the content of water in the system. The transit time distribution and its mean value serve for confirmation or determination of the conceptual model of the system and/or estimation of its potential vulnerability to anthropogenic pollution. In the interpretation of environmental tracer data with the aid of the lumped-parameter models, the influence of diffusion exchange between mobile water and stagnant or quasi-stagnant water is seldom considered, though it leads to large differences between tracer and water ages. Therefore, the article is focused on the transit time distribution functions of the most common lumped-parameter models, particularly those applicable for the interpretation of environmental tracer data in double-porosity aquifers, or aquifers in which aquitard diffusion may play an important role. A case study is recalled for a confined aquifer in which the diffusion exchange with aquitard most probably strongly influenced the transport of environmental tracers. Another case study presented is related to the interpretation of environmental tracer data obtained from lysimeters installed in the unsaturated zone with a fraction of stagnant water.

A field tracer test performed under natural flow conditions at the Twin Lake test site, Chalk River Laboratories of the Atomic Energy of Canada Ltd. in Chalk River, Ontario, Canada, using tritium and three herbicides (Chlor-toluron, Terbuthylazine, and Pendimethalin) was interpreted using the dispersion equation with a combined reaction model. The reaction model couples an instantaneous equilibrium reaction governed by a linear adsorption isotherm with a reversible or irreversible kinetic reaction of the first order, and decay. An improved interpretation method consists of a simultaneous fitting of theoretical concentration and mass-recovery curves to the experimental data, which leads to a more reliable determining of reaction models and improves the accuracy of fitting. Tritium served as the reference tracer to determine the flow velocity, dispersivity, and the recovery of the herbicides. Chlortoluron was slightly delayed by equilibrium exchange with strongly reduced concentration due to an irreversible kinetic reaction and/or decay. Terbuthilazine was slightly delayed by equilibrium exchange, with strongly reduced concentration due to a reversible kinetic reaction with some influence of decay. A strong equilibrium reaction and a strong reversible kinetic reaction without degradation governed the transport of Pendimethalin, reducing considerably its concentration. The results obtained show that simulations based only on Kd and decay constant, especially if these parameters are found in the laboratory, may considerably differ from those performed with reaction parameters determined in properly performed field tests. The dominant reaction types, and the values of parameters found in the study, supply useful information on the transport of the investigated herbicides in sandy aquifers under natural flow conditions.

A simple method to delineate the recharge areas of a series of springs draining a fractured aquifer is presented. Instead of solving the flow and transport equations, the delineation is reformulated as a mass balance problem assigning arable land in proportion to the pesticide mass discharged annually in a spring at minimum total transport cost. The approach was applied to the Luxembourg Sandstone, a fractured-rock aquifer supplying half of the drinking water for Luxembourg, using the herbicide atrazine. Predictions of the recharge areas were most robust in situations of strong competition by neighbouring springs while the catchment boundaries for isolated springs were extremely sensitive to the parameter controlling flow direction. Validation using a different pesticide showed the best agreement with the simplest model used, whereas using historical crop-rotation data and spatially distributed soil-leaching data did not improve predictions. The whole approach presents the advantage of integrating objectively information on land use and pesticide concentration in spring water into the delineation of groundwater recharge zones in a fractured-rock aquifer.

Summary The Diass horst aquifer system located 50 km east of Dakar (Senegal) is exploited in two main aquifers covered by a sandy superficial aquifer: the confined/unconfined Palaeocene karstic limestone and the confined Maastrichtian sandstone aquifer underneath. This system has experienced intensive groundwater abstraction during the last 50 years to supply increasing water demand, agricultural and industrial needs. The high abstraction rate from 1989 to 2009 (about 109,000 m 3 /d) has caused a continuous groundwater level decline (up to 30 m), a modification of the groundwater flow and salinization in parts of the aquifers. The objective of the study is to improve our understanding of the system functioning with regards to high pumping, identify the geochemical reactions that take place in the system, infer origin and timing of recharge by using mainly stable (δ 18 O, δ 2 H, 13 C) and radioactive ( 3 H and 14 C) isotopes. Water types defined in the Piper diagram vary in order of abundance from Ca–HCO 3 (65%), Ca/Na–Cl (20%), Na–HCO 3 (3%) and Na–Cl (12%). Values of δ 18 O and δ 2 H for the superficial aquifer range between −5.8 and −4.2‰ and between −42 and −31‰, respectively. For the Palaeocene aquifer they range from −5.8 to −5.0‰ and from −38 to −31‰, respectively; values in the Maastrichtian aquifer are between −5.9 and −4.3‰ for δ 18 O and −38 to −26‰ for δ 2 H. Plotted against the conventional δ 18 O vs δ 2 H diagram, data from the upper aquifer exhibit a dispersed distribution with respect to isotopic fractionation while those of the Palaeocene and Maastrichtian aquifers are aligned parallel and slightly below/or on the Global Meteoric Water Line (GMWL) evidencing ancient waters which had evaporated during infiltration. The low tritium (generally 14 C (0.7–57.2 pmc) contents indicate predominance of older water being recharged during the Pleistocene and Holocene periods. However, few boreholes which exhibit high tritium (1.2–4.3 TU) and 14 C (65.7–70.8 pmc) values indicate some mixture with recent water likely through faulting and vertical drainage from the upper to deeper aquifers as well as lateral flow along flow paths to the piezometric depressions created by pumping.

Pristine and energy-limited aquifers are considered to have a low resistance and resilience towards organic pollution. An experiment in an indoor aquifer system revealed an unexpected high intrinsic potential for the attenuation of a short-term toluene contamination. A 30h pulse of 486mg of toluene, used as a model contaminant, and deuterated water (D2O) through an initially pristine, oxic, and organic carbon poor sandy aquifer revealed an immediate aerobic toluene degradation potential. Based on contaminant and tracer break-through curves, as well as mass balance analyses and reactive transport modelling, a contaminant removal of 40% over a transport distance of only 4.2m in less than one week of travel time was obtained. The mean first-order degradation rate constant was λ=0.178day-1, corresponding to a half-life time constant T1/2 of 3.87days. Toluene-specific stable carbon isotope analysis independently proved that the contaminant mass removal can be attributed to microbial biodegradation. Since average doubling times of indigenous bacterial communities were in the range of months to years, the aerobic biodegradation potential observed is assumed to be present and active in the pristine, energy-limited groundwater ecosystems at any time. Follow-up experiments and field studies will help to quantify the immediate natural attenuation potential of aquifers for selected priority contaminants and will try to identify the key-degraders within the autochthonous microbial communities.

With the aim of studying the hydraulic behaviour and isotopic effects in refuse dumps, measurements of the 18O and 2H content of rainwater infiltrating into large cylindrical refuse lysimeters (1.5–4 m height with diameter of about 5 m), installed by the Technical University of Brunswick, Germany, were performed. The 11 lysimeters were filled with household refuse and sewage sludge under different conditions (aerobic/anaerobic, compaction, layering). The long-term hydraulic parameters of flow through the lysimeters (transit time, apparent dispersivity, volume of total water) were estimated with a specially adapted black-box model, which used isotopic content curves of rainwater and infiltrated water sampled at different depths in the lysimeters. The transit times of rainwater through the lysimeters (3–6 years) and the mean flow velocities deduced from them (0.4–1 m year−1), correspond to values in the unsaturated zone of sandy aquifers. The dispersivities are in the range of 0.1–1 cm. A special attempt was made to follow individual heavy rain events and estimate the travel times and portions of rainwater percolating swiftly through the lysimeter. It was found that up to 40% of those precipitation events drains off directly, i.e. within a few weeks. However, as it remains only a short time in the lysimeter, this water should not be greatly affected by the lysimeter filling. In addition, by evaluating the δ2H-δ18O relationship of the water samples from the different lysimeter sampling points, it was possible to differentiate, on a preliminary basis, isotopic effects caused by evaporation and biochemical reactions.

Neighboring springs draining fractured-rock aquifers can display large differences in water quality and flow regime, depending on local variations of the connectivity and the aperture size distribution of the fracture network. Consequently, because homogeneous equivalent parameters cannot be assumed a priori for the entire regional aquifer, the vulnerability to pollution of such springs has to be studied on a case by case basis. In this paper, a simple lumped-parameter model usually applied to estimate the mean transit time of water (or tracer) is presented. The original exponential piston-flow model was modified to take land-use distribution into account and applied to predict the evolution of atrazine concentration in a series of springs draining a fractured sandstone aquifer in Luxembourg, where despite a nationwide ban in 2005, atrazine concentrations still had not begun to decrease in 2009. This persistence could be explained by exponentially distributed residence times in the aquifer, demonstrating that in some real world cases, models based on the groundwater residence time distribution can be a powerful tool for trend reversal assessments as recommended for instance by current European Union guidelines.

Triassic carbonate aquifers in the Upper Silesia region, affected by intense withdrawal, have been investigated by means of isotopic analyses of (14)C, δ(13)C, δ(2)H, δ(18)O and (3)H. The isotopic examinations were carried out in the 1970s and in the early 1980s, and it was the first application of tracers to estimate age and vulnerability for the contamination of groundwater in this region. Similar isotopic analyses were conducted in 2007 and 2008 with the same Triassic carbonate formation. The isotopic examinations were performed within the confined part of the carbonate formation, wherein aquifers are covered by semi-permeable deposits. The direct recharge of the aquifer occurs in the outcrop areas, but it mainly takes place due to percolation of the water through aquitards and erosional windows. The Triassic aquifer has been intensively drained by wells and by lead-zinc mines. Nowadays, the declining water demand and closure of some mines have induced a significant increase in the water table level. The detailed analysis of the results, including the radiocarbon age corrections and the comparison of radioisotope activities, has made it possible to estimate the range of residence time within the carbonate Triassic aquifer. This range from several tens to several tens of thousands indicates that the recharge of aquifers might have occurred between modern times and the Pleistocene. The apparent age of the water estimated on the basis of (14)C activity was corrected considering the carbon isotope exchange and the diffusion between mobile water in fractures and stagnant water in micropores. The obtained corrected period of recharge corresponds to the result of investigations of noble gases, which were carried out in the 1990s. In almost half of the cases, groundwater is a mixture of young and old water. The mixing processes occur mainly in areas of heavy exploitation of the aquifer.

In the area of a planned dam site in the southern Black Forest, an observation tunnel with boreholes drilled into an adjacent vertically orientated ore body offered nearly ideal conditions to investigate transport phenomena in a highly permeable fault and fracture zone. The experimental array, consisting of horizontal and inclined boreholes lying within distances of ten to twelve meters apart, gave the opportunity to perform forced gradient tracer tests over varying distances under fixed hydraulic boundary conditions. The breakthrough curves of the tracer experiments were analyzed using an adequate transport model. The fitting procedure yielded hydraulic parameters such as fissure and matrix porosities and first estimations of the average fracture aperture.

Measurements of tritium and 18O concentrations in precipitation and runoff were used to provide further insight into the groundwater storage properties of the Wimbachtal Valley, a catchment area of 33.4 km2, extending between 636 and 2713 m a.s.l. in the Berchtesgaden Alps. The catchment includes three aquifer types: a dominant porous aquifer; a fractured dolomite; a karstic limestone aquifer. Employing a simple hydrological model, information about mean transit times of environmental tracers is derived for the groundwater runoff component and several karst springs from the application of the exponential and dispersion flow models to the isotopic input and output data. The mean transit times calculated from a dispersion model with transit times of 4.1 years for 18O and 4.2 years for tritium, which agree well, allow calculation of total (mobile + stagnant) groundwater storage volume, which is equivalent to 6.6 m of water depth. Direct runoff appears negligible as in many other cases.

The parallel fissure model coupled with the equation of diffusion into the matrix and with exchange reaction equations has been used to derive a simple formula for estimating the influence of matrix porosity and reaction parameters on the determination of radiocarbon ages in fissured carbonate rocks. Examples of evidently too great radiocarbon ages in carbonate formations, which are not explainable by models for the initial {sup 14}C corrections, can easily be explained by this formula. Parameters obtained for a chalk formation from a known multitracer experiment combined with a pumping test suggest a possibility of {sup 14}C ages more than three orders of magnitude greater than the ages which would be observed if the radiocarbon transport took place only in the mobile water in the fissures. It is shown that contrary to the solute movement on a small scale and with a variable input, the large-scale movement, characteristic for the {sup 14}C dating, does not necessarily require the knowledge of kinetic parameters, because they may be replaced by the distribution coefficient. Discordant tritium and {sup 14}C concentrations are commonly interpreted as a proof of mixing either in the aquifer or at the discharge site. For fissured carbonate formations, however, anmore » alternative explanation is given by the derived model showing a considerable delay of {sup 14}C with respect to nonsorbable tracers.« less

Groundwaters from the Quaternary and Continental Terminal Formations in the Nigeria sector of the Chad Sedimentary Basin (CSB) together with rain and surface waters have been chemically and isotopically analyzed in order to investigate sources and ages of waters, possible modern renewal and mixing of the deep groundwaters, and to infer palaeoclimate incidences. Most of the waters are slightly to moderately mineralized and are of Na-HCO 3 type induced mainly by Na-feldspar weathering and ion exchange reactions. The wide range of the δ 18 O and δ 2 H values and 3 H contents in the upper aquifer indicate replenishment with modern meteoric water. However, the deep system (middle and lower aquifers) with a narrow range of depleted stable isotope values and low 14 C activities indicates that these waters have a palaeometeoric origin. The period of infiltration was within the humid and cooler period (35 to 40 ka BP) prior to the Last Glacial Maximum. In addition, the isotope compositions of the deep system show no mixing with modern waters. These results are in agreement with other palaeorecord studies in the Sahel zone during this period.

[1] The spatial and temporal (event and seasonal timescale) variability of major runoff components in the mountainous Brugga basin (Black Forest, Germany) were examined. The mesoscale (40 km2) study basin represented an extraordinary challenge as comparable studies have been undertaken mainly in smaller headwater basins. Discharge data, tracer concentrations of 18O, 3H, CFCs, and dissolved silica, and major anions and cations were analyzed during single events and over a period of 3 years. Three main runoff components were defined: event water with a residence time of several hours to a few days contributed up to 50% during flood peaks, quantified by a classical hydrograph separation technique using 18O. However, this component is of minor importance for longer periods, comprising ∼11.1% of total runoff as estimated for the period August 1995 to April 1998. The other two flow components originated from shallow and deep groundwater. Source areas for these are the upper drift and debris cover for the shallow groundwater and the deeper drift, weathering zone and hard rock aquifer for the deep groundwater. Mean residence times ranged from 28 to 36 months on the basis of 18O data for the shallow groundwater and from 6 to 9 years on the basis of 3H and CFC data for the deep groundwater. The importance of the upper drift and debris cover of the slopes for runoff generation at the test site was clearly demonstrated at the seasonal timescale, showing a contribution of 69.4% based on a mixing model with a monthly time step. The deep groundwater contribution was 19.5%. With this information a conceptual model of runoff generation for the study site was constructed.

Two multitracer tests performed in one of the major cross-fault zones of the Lange Bramke basin (Harz Mountains, Germany) confirm the dominant role of the fault zone in groundwater flow and solute transport. Tracers having different coefficients of molecular diffusion (deuterium, bromide, uranine, and eosine) yielded breakthrough curves that can only be explained by a model that couples the advective–dispersive transport in the fractures with the molecular diffusion exchange in the matrix. For the scale of the tests (maximum distance of 225 m), an approximation was used in which the influence of adjacent fractures is neglected. That model yielded nearly the same rock and transport parameters for each tracer, which means that the single-fracture approximation is acceptable and that matrix diffusion plays an important role. The hydraulic conductivity of the fault zone obtained from the tracer tests is about 1.5×10–2 m/s, whereas the regional hydraulic conductivity of the fractured rock mass is about 3×10–7 m/s, as estimated from the tritium age and the matrix porosity of about 2%. These values show that the hydraulic conductivity along the fault is several orders of magnitude larger than that of the remaining fractured part of the aquifer, which confirms the dominant role of the fault zones as collectors of water and conductors of fast flow.

A model of parallel fractures, having equal spacing and width, has been applied to tracer movement in fissured rocks with a porous matrix. The exact solution has been obtained for instantaneous injection. Graphical presentations demonstrate the applicability and the limitations of particular approximations. In short-term experiments the single fracture approximation works well because the tracer has not penetrated the matrix deeply enough to be influenced by the adjacent fractures. In high matrix porosity, diffusion into the matrix is dominant and the model may be simplified by neglecting the influence of dispersivity. In low matrix porosity, a dispersion model with no diffusion into the matrix may often yield approximately the mean transit time of water. By contrast, in long-term tracer experiments, the tracer appears to exploit the whole water volume, i.e. both the mobile fissure volume and the stagnant micropore volume. The tracer curve yields the mean transit time of tracer, which is related to the mean transit time of water by the retardation factor. This factor is expressed approximately by the ratio of total porosity to fissure porosity, provided the tracer is non-adsorbable. For adsorbable tracers the microporosity acts as a strong sink due to the large adsorption surface. This fact is most probably the cause of the discrepancies observed between 14C ages in carbonate aquifers and the stable isotope shift expected from the climate change at the end of the last glaciation. It is also shown that the 14C exchange in carbonate rocks may yield 14C ages orders of magnitude too high in comparison with conventional flow data. Examples of the interpretation of artificial tracer experiments demonstrate that the model developed works surprisingly well.

Foreword About the editors List of all contributors Part 1 Groundwater quality 1 The role of the unsaturated zone in determining nitrate leaching to groundwater M. Matrocicco, N. Colombani, E. Salemi, F. Vincenzi & G. Castaldelli 2 Coupling an unsaturated model with a hydro-economic framework for deriving optimal fertilizer application to control nitrate pollution in groundwater S. Pena-Haro, F. Stauffer, C. Clementine & M. Pulido-Velazquez 3 Field tests for subsurface iron removal at a dairy farm in Saxony, Germany J.P. Ebermann, D. Eichhorn,W. Macheleidt, J.J. Ahrns & T. Grischek 4 DNA-microarrays for monitoring natural attenuation of emissions from abandoned landfill sites in contaminated groundwater plumes C. Charle, S. Kuhn & T. Struppe 5 Methodology for determining impacts on the chemical status of groundwater bodies: An application in a Mediterranean river basin (Southern Spain) D. Sanchez Garcia & F. Carrasco Cantos 6 Heavy metals removal from contaminated groundwater using permeable reactive barriers with immobilised membranes I. Zawierucha, C. Kozlowski & G. Malina 7 Event based monitoring and early warning system for groundwater resources in alpine karst aquifers H. Stadler, A. Leis,M. Plieschnegger, P. Skritek & A.H. Farnleitner 8 Cryopegs in theYakutian diamond-bearing province (Russia) S.V. Alexeev, L.P. Alexeeva & A.M. Kononov 9 Hydrogeological studies in diapiric-layering salt formation: The eastern part of the Catalonian Potassic Basin F. Ribera, H. Dorca, N. Otero, J. Palau & A. Soler 10 Hypogenic karst development in a hydrogeological context, Buda Thermal Karst, Budapest, Hungary A. Eross, J. Madl-Szonyi & A.E. Csoma 11 Geochemistry of thermal waters of the Sikhote-Alin ridge, Russia I.V. Bragin, G.A. Chelnokov & M.G. Blokhin 12 Arsenic in groundwater inWestern Anatolia,Turkey: A review O. Gunduz, A. Baba & H. Elpit Part 2 Groundwater management 13 Regional spatial-temporal assessment of the sustainability of groundwater exploitation in the south of Portugal T. Stigter, J.P. Monteiro, L. Nunes, L. Ribeiro & R. Hugman 14 Quality and quantity status and risk assessment of groundwater bodies in the karst areas of Croatia R. Biondic, B. Biondic, J. Rubinic & H. Measki 15 WEAP-MODFLOW as a Decision Support System (DSS) for integrated water resources management: Design of the coupled model and results from a pilot study in Syria J. Massmann, J.Wolfer, M. Huber, K. Schelkes,V. Hennings, A. Droubi & M. Al-Sibai 16 Groundwater recharge evaluation based on the infiltration method S. Stasko, R. Tarka & T. Olichwer 17 Seawater intrusion control by means of a reclaimed water injection barrier in the Llobregat delta, near Barcelona, Catalonia, Spain F. Ortuno, E. Custodio, J. Molinero, I. Juarez,T. Garrido & J. Fraile Part 3 Groundwater - surface water interaction 18 Sustainability of river bank filtration - examples from Germany T. Grischek, D. Schoenheinz, P. Eckert & C. Ray 19 Comparison of established methods to determine infiltration rates in river banks and lake shore sediments M. Soares, G. Gunkel & T. Grischek 20 Estimation of ratio of interception by shelterbelts from the saturated zone to evaporative loss A. Kedziora & D. Kayzer Part 4 Regional groundwater problems 21 Hydrogeological characterisation of the heterogeneity of aquitards from a multilayered system O. Cabaret, A. Dupuy & F. Larroque 22 Hydrogeological characterisation of two karst springs in Southern Spain by hydrodynamical data and intrinsic natural fluorescence J.A. Barbera & B. Andreo Part 5 Data processing & modelling 23 Integration of environmental tracer information with groundwater modelling F. Stauffer & W. Kinzelbach 24 Optimising groundwater monitoring networks using the particle swarm algorithm N. Ganji Khorramdel, S. Javadi, K. Mohammadi, K. Howard & M.J. Monem 25 A novel approach to groundwater model development T.D. Krom & R. Lane 26 Determining natural background values with probability plots T.Walter, A. Beer, D. Brose, D. Budziak, P. Clos,T. Dreher, H.-G. Fritsche, M. Hubschmann, S. Marczinek,A. Peters, H. Poeser, H.-J. Schuster, B.Wagner, F.Wagner, G. Wirsing & R.Wolter Author index Subject index SERIES IAH-Selected Papers