A new discrete model to better consider tracer distribution along boreholes during the Finite Volume Point Dilution Method.

The Finite Volume Point Dilution Method (FVPDM) is a single-well tracer experiment which has been successfully used in many hydrogeological contexts to quantify groundwater fluxes. During continuous injection of tracer into a well, the tracer concentration evolution measured within the tested well directly depends on the groundwater flow crossing the well screens. Up to now, the FVPDM mathematical formulation used to simulate the tracer concentration evolution measured in the tested well assumed perfect homogenization of the tracer along the tested interval, which is a reasonable assumption in many cases. However, when FVPDM are performed in long-screened boreholes or in very permeable aquifer materials, the recirculation flow rate imposed to ensure mixing is suspected to be too low to perfectly homogenize the tracer. In order to assess the effect of non-perfect mixing on FVPDM results, we introduce here a new discrete model that explicitly considers the recirculation flow rate. The mathematical developments are validated using field measurements, and a sensitivity analysis is proposed to assess the effect of the mixing flow rate on tracer concentration homogenization within the well. Results confirm that, when the recirculation flow rate applied is not high enough compared to the groundwater flow rate, the tracer distribution is not uniform in the tested interval. In this case, the use of the classical analytical solution, commonly used to interpret the concentration evolution leads to highly overestimated groundwater fluxes. The discrete model introduced here can be used instead to properly estimate groundwater fluxes and assess the tracer distribution within the tested interval. The discrete model offers the possibility of interpreting field measurements conducted under non-perfect mixing conditions and increases the range of fluxes that can be investigated through FVPDM.

Groundwater quality changes in peri-urban areas of the Walloon region of Belgium.

An extensive survey of groundwater quality was performed at the regional scale in peri-urban and industrial contexts of the Walloon Region (Belgium). To this end, 243 sampling locations from 8 areas located in different geological contexts and different peri-urban areas of the region were sampled outside pollution hotspots related to contaminated sites. Each groundwater sample was analyzed for 19 inorganic trace elements, 59 organic micro-pollutants and 8 major and minor elements. Five physico-chemical parameters were measured in the field, at the time of sampling to determine the environmental conditions prevailing in groundwater. Existing groundwater chemical data available outside such peri-urban and industrial areas were also compiled from existing groundwater quality databases for comparison. Most of the organic and inorganic pollutants are detected and their levels of occurrence are described statistically. Cumulative distribution function plots allow comparing the distributions of inorganic trace elements in and outside the urbanized and industrialized areas and among the different prevailing geological contexts. Two indicators are introduced, one quantifying the impact on inorganic trace elements of diffuse pollution in urban and industrial areas, the other reflecting the influence of lithology on concentrations in groundwater. Results show that the composition of groundwater is altered in peri-urban and industrial areas with increased concentrations for several organic pollutants and for most inorganic trace elements. However, the results clearly indicate that for the inorganic trace elements, anthropogenic influence is not limited to increased discharge of pollutants in the urban and industrial areas but also to significant changes in environmental conditions, with more reducing and acidic conditions observed in groundwater. The influence of lithology is also marked in the data set. From a more pragmatic point of view, the data set has been also used to derive upper limits of pollutant background concentrations to be used in decision-making related to the management of contaminated groundwater in urban and industrial environments in the Walloon Region.

Occurrence of greenhouse gases in the aquifers of the Walloon Region (Belgium).

This work aims to (1) identify the most conductive conditions for the generation of greenhouses gases (GHGs) in groundwater (e.g., hydrogeological contexts and geochemical processes) and (2) evaluate the indirect emissions of GHGs from groundwater at a regional scale in Wallonia (Belgium). To this end, nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations and the stable isotopes of nitrate (NO3-) and sulphate were monitored in 12 aquifers of the Walloon Region (Belgium). The concentrations of GHGs range from 0.05µg/L to 1631.2µg/L for N2O, 0µg/L to 17.1µg/L for CH4, and 1769 to 100,514ppm for the partial pressure of CO2 (pCO2). The highest average concentrations of N2O and pCO2 are found in a chalky aquifer. The coupled use of statistical techniques and stable isotopes is a useful approach to identify the geochemical conditions that control the occurrence of GHGs in the aquifers of the Walloon Region. The accumulation of N2O is most likely due to nitrification (high concentrations of dissolved oxygen and NO3- and null concentrations of ammonium) and, to a lesser extent, initial denitrification in a few sampling locations (medium concentrations of dissolved oxygen and NO3-). The oxic character found in groundwater is not prone to the accumulation of CH4 in Walloon aquifers. Nevertheless, groundwater is oversaturated with GHGs with respect to atmospheric equilibrium (especially for N2O and pCO2); the fluxes of N2O (0.32kgN2O-NHa-1y-1) and CO2 (27kgCO2Ha-1y-1) from groundwater are much lower than the direct emissions of N2O from agricultural soils and fossil-fuel-related CO2 emissions. Thus, indirect GHG emissions from the aquifers of the Walloon Region are likely to be a minor contributor to atmospheric GHG emissions, but their quantification would help to better constrain the nitrogen and carbon budgets.

Factors controlling spatial and temporal patterns of multiple pesticide compounds in groundwater (Hesbaye chalk aquifer, Belgium).

Factors governing spatial and temporal patterns of pesticide compounds (pesticides and metabolites) concentrations in chalk aquifers remain unclear due to complex flow processes and multiple sources. To uncover which factors govern pesticide compound concentrations in a chalk aquifer, we develop a methodology based on time series analyses, uni- and multivariate statistics accounting for concentrations below detection limits. The methodology is applied to long records (1996-2013) of a restricted compound (bentazone), three banned compounds (atrazine, diuron and simazine) and two metabolites (deethylatrazine (DEA) and 2,6-dichlorobenzamide (BAM)) sampled in the Hesbaye chalk aquifer in Belgium. In the confined area, all compounds had non-detects fractions >80%. By contrast, maximum concentrations exceeded EU's drinking-water standard (100 ng L-1) in the unconfined area. This contrast confirms that recent recharge and polluted water did not reach the confined area, yet. Multivariate analyses based on variables representative of the hydrogeological setting revealed higher diuron and simazine concentrations in the southeast of the unconfined area, where urban activities dominate land use and where the aquifer lacks protection from a less permeable layer of hardened chalk. At individual sites, positive correlations (up to τ=0.48 for bentazone) between pesticide compound concentrations and multi-annual groundwater level fluctuations confirm occurrences of remobilization. A downward temporal trend of atrazine concentrations likely reflects decreasing use of this compound over the last 28 years. However, the lack of a break in concentrations time series and maximum concentrations of atrazine, simazine, DEA and BAM exceeding EU's standard post-ban years provide evidence of persistence. Contrasting upward trends in bentazone concentrations show that a time lag is required for restriction measures to be efficient. These results shed light on factors governing pesticide compound concentrations in chalk aquifers. The developed methodology is not restricted to chalk aquifers, it could be transposed to study other pollutants with concentrations below detection limits.

Dynamics and emissions of N2O in groundwater: A review.

This work reviews the concentrations, the dynamics and the emissions of nitrous oxide (N2O) in groundwater. N2O is an important greenhouse gas (GHG) and the primary stratospheric ozone depleting substance. The major anthropogenic source that contributes to N2O generation in aquifers is agriculture because the use of fertilizers has led to the widespread groundwater contamination by inorganic nitrogen (N) (mainly nitrate, NO3-). Once in the aquifer, this inorganic N is transported and affected by several geochemical processes that produce and consume N2O. An inventory of dissolved N2O concentrations is presented and the highest concentration is about 18.000 times higher than air-equilibrated water (up to 4004µg N L-1). The accumulation of N2O in groundwater is mainly due to denitrification and to lesser extent to nitrification. Their occurrence depend on the geochemical (e.g., NO3-, dissolved oxygen, ammonium and dissolved organic carbon) as well as hydrogeological parameters (e.g., groundwater table fluctuations and aquifer permeability). The coupled understanding of both parameters is necessary to gain insight on the dynamics and the emissions of N2O in groundwater. Overall, groundwater indirect N2O emissions seem to be a minor component of N2O emissions to the atmosphere. Further research might be devoted to evaluate the groundwater contribution to the indirect emissions of N2O because this will help to better constraint the N2O global budget and, consequently, the N budget.

Multi-species measurements of nitrogen isotopic composition reveal the spatial constraints and biological drivers of ammonium attenuation across a highly contaminated groundwater system.

Groundwater under industrial sites is characterised by heterogeneous chemical mixtures, making it difficult to assess the fate and transport of individual contaminants. Quantifying the in-situ biological removal (attenuation) of nitrogen (N) is particularly difficult due to its reactivity and ubiquity. Here a multi-isotope approach is developed to distinguish N sources and sinks within groundwater affected by complex industrial pollution. Samples were collected from 70 wells across the two aquifers underlying a historic industrial area in Belgium. Below the industrial site the groundwater contained up to 1000 mg N l(-1) ammonium (NH4(+)) and 300 mg N l(-1) nitrate (NO3(-)), while downgradient concentrations decreased to ∼1 mg l(-1) DIN ([DIN] = [NH4(+)N] + [NO3(-)N] + [NO2(-)N]). Mean δ(15)N-DIN increased from ∼2‰ to +20‰ over this flow path, broadly confirming that biological N attenuation drove the measured concentration decrease. Multi-variate analysis of water chemistry identified two distinct NH4(+) sources (δ(15)NNH4(+) from -14‰ and +5‰) within the contaminated zone of both aquifers. Nitrate dual isotopes co-varied (δ(15)N: -3‰ - +60‰; δ(18)O: 0‰ - +50‰) within the range expected for coupled nitrification and denitrification of the identified sources. The fact that δ(15)NNO2(-) values were 50‰-20‰ less than δ(15)NNH4(+) values in the majority of wells confirmed that nitrification controlled N turnover across the site. However, the fact that δ(15)NNO2(-) was greater than δ(15)NNH4(+) in wells with the highest [NH4(+)] shows that an autotrophic NO2(-) reduction pathway (anaerobic NH4(+) oxidation or nitrifier-denitrification) drove N attenuation closest to the contaminant plume. This direct empirical evidence that both autotrophic and heterotrophic biogeochemical processes drive N attenuation in contaminated aquifers demonstrates the power of multiple N isotopes to untangle N cycling in highly complex systems.

Use of dual carbon-chlorine isotope analysis to assess the degradation pathways of 1,1,1-trichloroethane in groundwater.

Compound-specific isotope analysis (CSIA) is a powerful tool to track contaminant fate in groundwater. However, the application of CSIA to chlorinated ethanes has received little attention so far. These compounds are toxic and prevalent groundwater contaminants of environmental concern. The high susceptibility of chlorinated ethanes like 1,1,1-trichloroethane (1,1,1-TCA) to be transformed via different competing pathways (biotic and abiotic) complicates the assessment of their fate in the subsurface. In this study, the use of a dual C-Cl isotope approach to identify the active degradation pathways of 1,1,1-TCA is evaluated for the first time in an aerobic aquifer impacted by 1,1,1-TCA and trichloroethylene (TCE) with concentrations of up to 20 mg/L and 3.4 mg/L, respectively. The reaction-specific dual carbon-chlorine (C-Cl) isotope trends determined in a recent laboratory study illustrated the potential of a dual isotope approach to identify contaminant degradation pathways of 1,1,1-TCA. Compared to the dual isotope slopes (Δδ(13)C/Δδ(37)Cl) previously determined in the laboratory for dehydrohalogenation/hydrolysis (DH/HY, 0.33 ± 0.04) and oxidation by persulfate (∞), the slope determined from field samples (0.6 ± 0.2, r(2) = 0.75) is closer to the one observed for DH/HY, pointing to DH/HY as the predominant degradation pathway of 1,1,1-TCA in the aquifer. The observed deviation could be explained by a minor contribution of additional degradation processes. This result, along with the little degradation of TCE determined from isotope measurements, confirmed that 1,1,1-TCA is the main source of the 1,1-dichlorethylene (1,1-DCE) detected in the aquifer with concentrations of up to 10 mg/L. This study demonstrates that a dual C-Cl isotope approach can strongly improve the qualitative and quantitative assessment of 1,1,1-TCA degradation processes in the field.

Physically based groundwater vulnerability assessment using sensitivity analysis methods.

A general physically based method is presented to assess the vulnerability of groundwater to external pressures by numerical simulation of groundwater flow. The concept of groundwater vulnerability assessment considered here is based on the calculation of sensitivity coefficients for a user-defined groundwater state for which we propose several physically based indicators. Two sensitivity analysis methods are presented: the sensitivity equation method and the adjoint operator method. We show how careful selection of a method can significantly minimize the computational effort. An illustration of the general methodology is presented for the Herten aquifer analog (Germany). This application to a simple, yet insightful, case demonstrates the potential use of this general and physically based vulnerability assessment method to complex aquifers.

Is it worth protecting groundwater from diffuse pollution with agri-environmental schemes? A hydro-economic modeling approach.

In Europe, 30% of groundwater bodies are considered to be at risk of not achieving the Water Framework Directive (WFD) 'good status' objective by 2015, and 45% are in doubt of doing so. Diffuse agricultural pollution is one of the main pressures affecting groundwater bodies. To tackle this problem, the WFD requires Member States to design and implement cost-effective programs of measures to achieve the 'good status' objective by 2027 at the latest. Hitherto, action plans have mainly consisted of promoting the adoption of Agri-Environmental Schemes (AES). This raises a number of questions concerning the effectiveness of such schemes for improving groundwater status, and the economic implications of their implementation. We propose a hydro-economic model that combines a hydrogeological model to simulate groundwater quality evolution with agronomic and economic components to assess the expected costs, effectiveness, and benefits of AES implementation. This hydro-economic model can be used to identify cost-effective AES combinations at groundwater-body scale and to show the benefits to be expected from the resulting improvement in groundwater quality. The model is applied here to a rural area encompassing the Hesbaye aquifer, a large chalk aquifer which supplies about 230,000 inhabitants in the city of Liege (Belgium) and is severely contaminated by agricultural nitrates. We show that the time frame within which improvements in the Hesbaye groundwater quality can be expected may be much longer than that required by the WFD. Current WFD programs based on AES may be inappropriate for achieving the 'good status' objective in the most productive agricultural areas, in particular because these schemes are insufficiently attractive. Achieving 'good status' by 2027 would demand a substantial change in the design of AES, involving costs that may not be offset by benefits in the case of chalk aquifers with long renewal times.

Regional transport modelling for nitrate trend assessment and forecasting in a chalk aquifer.

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 50mg/l; however, even in that case, more than 50 years is needed to fully reverse upward trends.

Comparison of methods for the detection and extrapolation of trends in groundwater quality.

Land use changes and the intensification of agriculture since the 1950s have resulted in a deterioration of groundwater quality in many European countries. For the protection of groundwater quality, it is necessary to (1) assess the current groundwater quality status, (2) detect changes or trends in groundwater quality, (3) assess the threat of deterioration and (4) predict future changes in groundwater quality. A variety of approaches and tools can be used to detect and extrapolate trends in groundwater quality, ranging from simple linear statistics to distributed 3D groundwater contaminant transport models. In this paper we report on a comparison of four methods for the detection and extrapolation of trends in groundwater quality: (1) statistical methods, (2) groundwater dating, (3) transfer functions, and (4) deterministic modeling. Our work shows that the selection of the method should firstly be made on the basis of the specific goals of the study (only trend detection or also extrapolation), the system under study, and the available resources. For trend detection in groundwater quality in relation to diffuse agricultural contamination, a very important aspect is whether the nature of the monitoring network and groundwater body allows the collection of samples with a distinct age or produces samples with a mixture of young and old groundwater. We conclude that there is no single optimal method to detect trends in groundwater quality across widely differing catchments.

A new tracer technique for monitoring groundwater fluxes: the Finite Volume Point Dilution Method.

Quantification of pollutant mass fluxes is essential for assessing the impact of contaminated sites on their surrounding environment, particularly on adjacent surface water bodies. In this context, it is essential to quantify but also to be able to monitor the variations with time of Darcy fluxes in relation with changes in hydrogeological conditions and groundwater - surface water interactions. A new tracer technique is proposed that generalizes the single-well point dilution method to the case of finite volumes of tracer fluid and water flush. It is called the Finite Volume Point Dilution Method (FVPDM). It is based on an analytical solution derived from a mathematical model proposed recently to accurately model tracer injection into a well. Using a non-dimensional formulation of the analytical solution, a sensitivity analysis is performed on the concentration evolution in the injection well, according to tracer injection conditions and well-aquifer interactions. Based on this analysis, optimised field techniques and interpretation methods are proposed. The new tracer technique is easier to implement in the field than the classical point dilution method while it further allows monitoring temporal changes of the magnitude of estimated Darcy fluxes, which is not the case for the former technique. The new technique was applied to two experimental sites with contrasting objectives, geological and hydrogeological conditions, and field equipment facilities. In both cases, field tracer concentrations monitored in the injection wells were used to fit the calculated modelled concentrations by adjusting the apparent Darcy flux crossing the well screens. Modelling results are very satisfactory and indicate that the methodology is efficient and accurate, with a wide range of potential applications in different environments and experimental conditions, including the monitoring with time of changes in Darcy fluxes.

Modelling the migration of contaminants through variably saturated dual-porosity, dual-permeability chalk.

In the Hesbaye region in Belgium, tracer tests performed in variably saturated fissured chalk rocks presented very contrasting results in terms of transit times, according to artificially controlled water recharge conditions prevailing during the experiments. Under intense recharge conditions, tracers migrated across the partially or fully saturated fissure network, at high velocity in accordance with the high hydraulic conductivity and low effective porosity (fracture porosity). At the same time, a portion of the tracer was temporarily retarded in the almost immobile water located in the matrix. Under natural infiltration conditions, the fissure network remained inactive. Tracers migrated downward through the matrix, at low velocity in relation with the low hydraulic conductivity and the large porosity of the matrix. Based on these observations, Brouyère et al. (2004a) [Brouyère, S., Dassargues, A., Hallet, V., 2004a. Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation, J. Contam. Hydrol., 72 (1-4), 135-164, doi: 10.1016/j.conhyd.2003.10.009] proposed a conceptual model in order to explain the migration of solutes in variably saturated, dual-porosity, dual-permeability chalk. Here, mathematical and numerical modelling of tracer and contaminant migration in variably saturated fissured chalk is presented, considering the aforementioned conceptual model. A new mathematical formulation is proposed to represent the unsaturated properties of the fissured chalk in a more dynamic and appropriate way. At the same time, the rock water content is partitioned between mobile and immobile water phases, as a function of the water saturation of the chalk rock. The groundwater flow and contaminant transport in the variably saturated chalk is solved using the control volume finite element method. Modelling the field tracer experiments performed in the variably saturated chalk shows the adequacy and usefulness of the new conceptual, mathematical and numerical model.

Influence of injection conditions on field tracer experiments.

Calibration of ground water transport models is often performed using results of field tracer experiments. However, little attention is usually paid to the influence, on resulting breakthrough curves, of injection conditions and well-aquifer interactions, more particularly of the influence of the possible trapping of the tracer in the injection wellbore. Recently, a new mathematical and numerical approach has been developed to model injection conditions and well-aquifer interactions in a very accurate way. Using an analytical solution derived from this model, a detailed analysis is made of the evolution of the tracer input function in the aquifer. By varying injection conditions from one simulation to another, synthetic breakthrough curves are generated with the SUFT3D ground water flow and transport finite-element simulator. These tests show clearly that the shape of the breakthrough curves can be dramatically affected by injection conditions. Using generated breakthrough curves as "actual" field results, a calibration of hydrodispersive parameters is performed, neglecting the influence of injection conditions. This shows that neglecting the influence of actual injection conditions can lead to (1) errors on fitted parameters and (2) misleading identification of the active transport processes. Conclusions and guidelines are drawn in terms of proposed methodologies for better controlling the tracer injection in the field, in order to minimize risk of misinterpretation of results.

Migration of contaminants through the unsaturated zone overlying the Hesbaye chalky aquifer in Belgium: a field investigation.

This paper presents the results of a detailed field investigation that was performed for studying groundwater recharge processes and solute downward migration mechanisms prevailing in the unsaturated zone overlying a chalk aquifer in Belgium. Various laboratory measurements were performed on core samples collected during the drilling of boreholes in the experimental site. In the field, experiments consisted of well logging, infiltration tests in the unsaturated zone, pumping tests in the saturated zone and tracer tests in both the saturated and unsaturated zones. Results show that gravitational flows govern groundwater recharge and solute migration mechanisms in the unsaturated zone. In the variably saturated chalk, the migration and retardation of solutes is strongly influenced by recharge conditions. Under intense injection conditions, solutes migrate at high speed along the partially saturated fissures, downward to the saturated zone. At the same time, they are temporarily retarded in the almost immobile water located in the chalk matrix. Under normal recharge conditions, fissures are inactive and solutes migrate slowly through the chalk matrix. Results also show that concentration dynamics in the saturated zone are related to fluctuations of groundwater levels in the aquifer. A conceptual model is proposed to explain the hydrodispersive behaviour of the variably saturated chalk. Finally, the vulnerability of the chalk to contamination issues occurring at the land surface is discussed.