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...

Contaminants like nitroaromatic compounds can be degraded in the subsurface to similar or even more toxic metabolites. Degradation or transformation rates are dependent on physical, chemical and biological properties which can be different in sedimentological layers or other heterogeneous structures of aquifers. Sediments with low hydraulic conductivity can even consist of immobile water. These regions are only accessible by diffusion. Most modelling approaches accounting for immobile water regions focused on the mathematical description of the transport and decay of the parent compound. The objective of this study was to develop an analytical model to quantify the transport and formation of a metabolite in dual-porosity media describing the exchange between mobile and immobile water regions based on the metabolite's diffusion coefficient. Column experiments with a well-defined immobile water region were performed under anoxic conditions at three different water flow velocities. The model compound 4-Cl-nitrobenzene was reduced to 4-Cl-aniline (4-Cl-An) by surface-bound Fe (II) species within the immobile water region. Transport and formation of the metabolite were quantified with a modified solution of the single fissure dispersion model assuming additionally for the region with immobile water first-order metabolite production, irreversible sorption and an instantaneous equilibrium sorption. The number of unknown fitting parameters was reduced to two (sorption rate and retardation factor) by stepwise parameter estimation using tracer and parent compound data. Experimental results of the metabolite for each water flow velocity were successfully described with a first-order production term (λ prod = 1.51 ± 0.08 h-1), retardation factor (R im = 2.94 ± 0.45) and first-order irreversible sorption rate (K im = 0.39 ± 0.16 h-1) within the immobile water region. Model results supported that 4-Cl-An was formed within the immobile water region. 4-Cl-An sorbed instantaneously onto the clay matrix while a fraction was irreversibly sorbed. Experimental results and the provided analytical solution help to improve the understanding about reactive transport and the formation of metabolites in dual-porosity media.

Variable density flow in porous media has been studied primarily using numerical models because it is a semi-chaotic and transient process. Most of these studies have been 2D, owing to the computational restrictions on 3D simulations, and the ability to observe variable density flow in 2D experimentation. However, it is recognised that variable density flow is a three-dimensional process. A 3D system may cause weaker variable density flow than a 2D system due to stronger dispersion, but may also result in bigger fingers and hence stronger variable density flow because of more space for fingers to coalesce. This study aimed to determine the representativeness of 2D modelling to simulate 3D variable density flow. 3D homogeneous sand column experiments were conducted at three different water flow velocities with three different bromide tracer solutions mixed with methanol resulting in different density ratios. Both 2D axisymmetric and 3D numerical simulations were performed to reproduce experimental data. Experimental results showed that the magnitude of variable density flow increases with decreasing flow rates and decreasing density ratios. The shapes of the observed breakthrough curves differed significantly from those produced by 2D axisymmetric and 3D simulations. Compared to 2D simulations, the onset of instabilities was delayed but the growth was more pronounced in 3D simulations. Despite this difference, both 2D axisymmetric and 3D models successfully simulated mass recovery with high efficiency (between 77% and 99%). This study indicates that 2D simulations are sufficient to understand integrated features of variable density flow in homogeneous sand column experiments.

Nitroaromatic compounds (NACs) are reduced by structural or surface bound Fe (II) species under anaerobic conditions in the subsurface. This reaction preferentially occurs on clay minerals which are mainly present in areas with low hydraulic conductivity containing nearly immobile water. Diffusion is the dominating transport process in these zones. Due to the complexity in such heterogeneous systems, the mathematical prediction of reactive solute transport taking into account diffusive mass exchange into immobile water regions still remains challenging. Therefore, the influence of immobile water regions on the fate of 4-Cl-Nitrobenzene (4-Cl-Nb) was quantified in dual-porosity column experiments at three different mean transit times under saturated anaerobic conditions in the presence of soluble Fe (II). A multi-tracer approach and a Single Fissure Dispersion Model (SFDM) were used to estimate input parameter to further model the transport of 4-Cl-Nb. Reactive solute transport of 4-Cl-Nb was quantified considering instantaneous sorption on to the clay matrix and a reduction within the immobile water region following first-order kinetics. The experimental results indicated that sorption onto the clay matrix enhanced the mass exchange of 4-Cl-Nb into immobile water region compared to nonreactive solutes. At the same time the abiotic reduction of 4-Cl-Nb limited the process of back diffusion to mobile water regions. Fitted retardation factors (Rim = 4.62 ± 0.68) and decay rates (k = 1.51 ± 0.08 h− 1) were independent on tested flow velocities. Findings of this study can advance the understanding on the fate of NACs in the subsurface which is essential for prediction of reactive solute transport at field scale.

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.

Applications of simple lumped parameter models to describe aspects of hydrological systems rest on assumptions of homogeneity that are rarely valid. The lumped parameters are supposed to represent the quantities within the system as well as those of the overall system, but such quantities will obviously vary greatly from place to place within heterogeneous systems. Less appreciated is the fact that aggregation errors will affect overall system parameters as well. Kirchner (2016a) recently demonstrated that aggregation errors due to heterogeneity in catchments could cause severe underestimation of the mean transit times (MTTs) of water travelling through catchments when simple lumped parameter models were applied to interpret seasonal tracer cycles. Here we examine the effects of such errors on the MTTs and young water fractions estimated using tritium concentrations. We find that MTTs derived from tritium concentrations in streamflow are just as susceptible to aggregation bias as those from seasonal tracer cycles. Likewise, groundwater wells or springs fed by two or more water sources with different MTTs will also show aggregation bias. However, the transit times over which the biases are manifested are very different; for seasonal tracer cycles it is 2–3 months up to about 5 years, while for tritium concentrations it is 6–12 years up to about 200 years. We also find that young water fractions derived from tritium are almost immune to aggregation errors as were those derived from seasonal tracer cycles. To investigate the implications of these findings for past and future use of tritium for estimating MTTs in catchments and groundwater systems, we examined case studies from the literature in which simple and more complicated lumped parameter models had been used. We find that MTT aggregation errors are small when either component waters are young (less than 6–12 years, as found in many catchments), or component waters have similar MTTs to each other. On the other hand, aggregation errors are large when very young water components are mixed with old components. In general, well-chosen compound lumped parameter models should be used as they will eliminate potential aggregation errors due to the application of simple lumped parameter models. The choice of a suitable lumped parameter model can be assisted by matching simulations to time series of tritium measurements (underlining the value of long series of tritium measurements), but such results should also be finally validated to ensure that the parameters found by modelling correspond to reality.