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Groundwater recharge (GR) is a complex process that is difficult to quantify. Increasing attention has been given to unsaturated zone modeling to estimate GR and better understand the processes controlling it. Continuous soil-moisture time series have been shown to provide valuable information in this regard. The objectives of this study were to (i) analyze the processes and factors controlling GR in an unconfined granular aquifer in a cold and humid environment and (ii) assess the uncertainties associated with the use of data from different sources. Soil moisture data monitored over three years at three experimental sites in southern Quebec (Canada) were used to calibrate the HYDRUS-1D model and to estimate ranges of possible GR in a region where groundwater is increasingly used as a source of fresh water. The simulations identified and quantified important factors responsible for the near-surface water balance that leads to GR. The resulting GR estimates from 2016 to 2018 showed marked differences between the three sites, with values ranging from 347 to 735 mm/y. Mean GR for the three sites was 517 mm/y for 2016–2018 and 455 mm/y for the previous 12-year period. GR was shown to depend on monthly variations in precipitation and on soil textural parameters in the root zone, both controlling soil-water retention and evapotranspiration. Monthly recharge patterns showed distinct preferential GR periods during the spring snowmelt (38–45% of precipitation) and in the fall (29% of precipitation). The use of different meteorological datasets was shown to influence the GR estimates.

Seasonal snowpack deeply influences the distribution of meltwater among watercourses and groundwater. During rain-on-snow (ROS) events, the structure and properties of the different snow and ice layers dictate the quantity and timing of water flowing out of the snowpack, increasing the risk of flooding and ice jams. With ongoing climate change, a better understanding of the processes and internal properties influencing snowpack outflows is needed to predict the hydrological consequences of winter melting episodes and increases in the frequency of ROS events. This study develops a multi-method approach to monitor the key snowpack properties in a non-mountainous environment in a repeated and non-destructive way. Snowpack evolution during the winter of 2020–2021 was evaluated using a drone-based, ground-penetrating radar (GPR) coupled with photogrammetry surveys conducted at the Ste-Marthe experimental watershed in Quebec, Canada. Drone-based surveys were performed over a 200 m2 area with a flat and a sloped section. In addition, time domain reflectometry (TDR) measurements were used to follow water flow through the snowpack and identify drivers of the changes in snowpack conditions, as observed in the drone-based surveys. The experimental watershed is equipped with state-of-the-art automatic weather stations that, together with weekly snow pit measurements over the ablation period, served as a reference for the multi-method monitoring approach. Drone surveys conducted on a weekly basis were used to generate georeferenced snow depth, density, snow water equivalent and bulk liquid water content maps. Despite some limitations, the results show that the combination of drone-based GPR, photogrammetric surveys and TDR is very promising for assessing the spatiotemporal evolution of the key hydrological characteristics of the snowpack. For instance, the tested method allowed for measuring marked differences in snow pack behaviour between the first and second weeks of the ablation period. A ROS event that occurred during the first week did not generate significant changes in snow pack density, liquid water content and water equivalent, while another one that happened in the second week of ablation generated changes in all three variables. After the second week of ablation, differences in density, liquid water content (LWC) and snow water equivalent (SWE) between the flat and the sloped sections of the study area were detected by the drone-based GPR measurements. Comparison between different events was made possible by the contact-free nature of the drone-based measurements.

This study proposes a simple isotopic framework for the identification of riverbank filtration wells, using time-series of water’s stable isotopes and electrical conductivity at the watershed scale. Riverbank-filtration (RBF) is a widely used managed aquifer recharge method where the infiltration of surface water is induced by pumping groundwater at proximity of a river or lake, and where the quality of the raw water is controlled by the interaction between ground and surface water bodies. As inventories of RBF sites are rare, they limit the development of specific source protection strategies. In the framework of a project funded by the Ministry of the Environment and the Fight against Climate Change of Québec (MELCC, Canada), 40 municipal wells located at less than 500 meters from a surface water body were sampled for 18 months on a monthly to weekly basis. The underlying hypothesis was that a significant contribution of infiltrated surface water to a pumping well would propagate the temporal variations of the tracers observed in surface water. Results highlighted that 25% of the wells pumped a significant contribution of infiltrated surface water: 15% established a continuous connection during the whole hydrological year, while the other 10% revealed a seasonal connection linked to spring floods. All those wells were located less than 120 meters from the surface water and drilled less than 40 meters deep in a granular aquifer. As the number and strength of spring floods may increase in the future, the seasonally connected wells are particularly vulnerable to global change and might prefigure increasing climate forcing on drinking water supply. The remaining 75% were either evidenced as groundwater only (50%) or lacked continuity in the data acquisition (25%). A simple abacus based on the standard deviation of the tracer distribution was then proposed to facilitate the interpretation and make the methods accessible to all. Based on an affordable and easy to perform sampling protocol for water managers, this framework helps in the assessment of specific risks associated to mixed sources of water, and in anticipating variations in quality of the abstracted drinking water.

In the critical zone, infiltrated surface water within porous media drives many biogeochemical processes that lead to a natural attenuation of contaminants. In the case of induced bank filtration (IBF), quantifying residence time is required to anticipate water quality issues. Due to combined hydroclimatic regimes and variable pumping sequences, groundwater flow is unsteady and classical residence time quantification approaches often fail to account for such dynamics. Radium is a geogenic element with four isotopes offering ideal half-life ranges for estimating groundwater residence time. Its potential to characterize water mixing processes or date seawater has been widely proven. These advances were supported by the development of affordable analysis devices such as delayed coincidence counters (RaDeCC). In freshwater, the radium adsorption ability on the porous matrix affects its mobility and reduces its availability in dissolved form. These direct consequences of adsorption i) restrict the representativity of water samples, ii) impact the ability to measure dissolved radium by RaDeCC and iii) drastically reduce the temporal range for using radium as a chronometer of surface water residence time in an aquifer. Without a paradigm change, radium as a temporal tracer in freshwater won’t reveal its full potential. However, the third point may be appropriate for tracing dynamics of unsteady flow such as those prevailing for infiltrated surface water in IBF site. A two-years study led in an IBF site equipped with eight wells and 10 piezometers allowed 200 samples to be analysed with a RaDeCC for 223, 224, 228 and 226 radium isotopes. Preliminary results suggest that dissolved radium is more controlled by flow than by a differential adsorption, as no clear correlation was found between dissolved radium and geochemistry (ORP, pH, EC). The spatial distribution pattern of short-lived isotopes at the site was related to the pumping regimes. Annual amplitudes of dissolved radium isotopes presented a periodicity for all the wells. These first results show a satisfactory tracer response to spatial and temporal hydrodynamic flow changes, either from natural or anthropogenic origin in critical zone.

In the Lake Winnipeg Basin (LWB), at both basin and regional scales, there are currently gaps regarding the significance of groundwater as a mediator of nutrient and contaminant fluxes to Lake Winnipeg. During 2018, surface water and groundwater samples were collected from various locations across the largest sand and gravel aquifer (Assiniboine Delta Aquifer [ADA]; 3800 km2) in the LWB as well as from surface water courses flowing above this aquifer. The samples collected during spring and fall were analyzed for anions and cations as well as for a series of isotopic and geochemical tracers (e.g. water isotopes, carbon 14, artificial sweeteners, pesticides, etc.). The results reveal that groundwater and the small watercourses flowing above the ADA have a similar chemical composition, which is in contrast with the chemical composition of the main watercourse flowing above the aquifer (Assiniboine River [AR]). When corroborated with stream discharge measurements this indicates that groundwater plays a significant role at local scale in controlling both the flow and the chemical composition of the AR tributaries. Nitrate showed low to non-detectable concentrations in both groundwater and surface water. With respect to groundwater, this could be related to the reducing conditions in the deeper aquifer in conjunction with relatively large groundwater travel times of up to 2400 years.

Seasonal snowpack deeply influences the distribution of meltwater among watercourses and groundwater. During rain-on-snow (ROS) events, for instance, the structure and properties of the different ice and snow layers dictate the quantity of water flowing out of the snowpack, increasing the risk of flooding and ice jams. With ongoing climate change, a better understanding of the processes and internal properties influencing snowpack outflows is needed to predict the hydrological consequences as mild episodes and ROS events’ frequency increases. This study aims to develop a multi-method approach to monitor the key snowpack properties in a non-mountainous environment in a repetitive and non-destructive way. Snowpack evolution was evaluated using a combination of drone-based GPR, photogrammetry surveys and time domain reflectometry (TDR) measurements, tested during the winter of 2020–2021 at the Sainte-Marthe experimental watershed, Quebec, Canada. The experimental watershed is equipped with state-of-the-art automatic weather stations that, together with weekly snow pit measurements, serve as a reference for the multi-method monitoring approach. Drone surveys conducted on a weekly basis are used to generate georeferenced snow depth, relative density, snow water equivalent and average liquid water content maps. In between site visits, snowpack properties are monitored using TDR probes. Despite some limitations, the results show that the approach is very promising in assessing the spatiotemporal evolution of the key hydrological characteristics of the snowpack. Among others, results showed the prevalence of preferential pathways at the early stage of the ablation period, the difference in hydrological reaction to a ROS event between flat and sloped sections of the study area and the hydrological influence of solar radiation at the late stage of the ablation period.

Identifying groundwater wells performing riverbank filtration (RBF) is crucial to ensure safe drinking water through vulnerability assessment plans adapted to these hybrid water sources. Nonetheless, RBF is often unintentional or insufficiently documented and official inventories are scarce. We developed a user-friendly geochemical and isotopic framework for the in-situ identification of RBF facilities. It includes an interpretation abacus for non-specialists. While most studies using tracers are site-specific and/or based on discrete samples, we propose a novel multi-site characterization where time-series of EC, δ

International audience; Modeling water and solute transport in the vadose zone for groundwater resource management requires an accurate determination of soil hydraulic parameters. Estimating these parameters by inverse modeling using in situ observations is very common. However, little attention has been given to the potential of pore water isotope information to parameterize soil water transport models. By conducting a Morris and Sobol sensitivity analysis, we highlight the interest of combining water content and pore water isotope composition data in a multi-objective calibration approach to constrain soil hydraulic property parameterization. We then investigate the effect of the sampling frequency of the observed data used for model calibration on a synthetic case. When modeling is employed in order to estimate the annual groundwater recharge of a sandy aquifer, it is possible to calibrate the model without continuous monitoring data, using only water content and pore water isotopic composition profiles from a single sampling time. However, even if not continuous, multi-temporal data improve model calibration, especially pore water isotope data. The proposed calibration method was validated with field data. For groundwater recharge estimate studies, these results imply a significant reduction in the time and effort required, by avoiding long-term monitoring, since only one sampling campaign is needed to extract soil samples.

Oil and gas well leakage is of public concern primarily due to the perceived risks of aquifer contamination and greenhouse gas (GHG) emissions. This study examined well leakage data from the British Columbia Oil and Gas Commission (BC OGC) to identify leakage pathways and initially quantify incident rates of leakage and GHG emissions from leaking wells. Three types of leakage are distinguished: “surface casing vent flow” (SCVF), “outside the surface casing leakage” (OSCL), and “cap leakage” (CL). In British Columbia (BC), the majority of reported incidents involve SCVF of gases, which does not pose a risk of aquifer contamination but does contribute to GHG emissions. Reported liquid leakage of brines and hydrocarbons is rarer. OSCL and CL of gas are more serious problems due to the risk of long-term leakage from abandoned wells; some were reported to be leaking gas several decades after they were permanently abandoned. According to the requirements of provincial regulation, 21,525 have been tested for leakage. In total, 2,329 wells in BC have had reported leakage during the lifetime of the well. This represents 10.8% of all wells in the assumed test population. However, it seems likely that wells drilled and/or abandoned before 2010 have unreported leakage. In BC, the total GHG emission from gas SCVF is estimated to reach about 75,000 t/y based on the existing inventory calculation; however, this number is likely higher due to underreporting.

Interactions between groundwater and surface water are often overlooked in lake water budgets, even though groundwater can significantly contribute to the total annual water inputs to a lake. Isotope mass balance models have seen significant developments in the last decade for assessing the spatial and temporal variability of hydrological processes in lakes but are generally applied assuming steady-state. While this assumption is generally acceptable for long-term water balances of large lakes, it may be less appropriate for lakes which undergo strong seasonality of hydrological processes and meteorological conditions. In this study, a volume-dependent transient isotopic mass balance model was developed for an artificial lake (named Lake A) in Canada, and in a context where direct measurement of surface water fluxes is difficult, if not impossible. This lake typically receives important inputs of flood-water during the spring freshet period, as a hydraulic connection with a large watershed establishes each year. Quantification of the water fluxes to Lake A allowed to highlight the impacts of flood-water inputs over the annual water budget. The isotopic mass balance model revealed that groundwater and surface water inputs respectively account for 71 % and 28 % of the total annual water inputs to Lake A, which demonstrates its dependence on groundwater. An important part of these groundwater inputs is likely to correspond to flood-derived surface water due to bank storage. On an annual timescale, Lake A was found to be resilient to surface water pollution and sensitive to groundwater quantity and quality changes. There is however a likelihood that the resilience to surface water pollution is lower from April to August, as important water inputs originating from Lake DM contribute to the water balance via direct and indirect inputs (i.e., from bank storage). This suggests that the surface water fluxes between Lake DM and Lake A did not only have an impact on the dynamic of Lake A during springtime but also significantly influenced the long-term dynamics of Lake A. These findings can help anticipating the impacts of variation in the intensity and/or duration of future flooding events on lakes' water quality. From a more global perspective, this knowledge is useful for establishing regional-scale management strategies for maintaining water quality at flood-affected lakes in a context of land-use and climate changes.

Krypton-85 and other radioactive noble gases are widely used for groundwater dating purposes. 85Kr analysis require large volumes of water to reach the analytical requirements. Conventionally, this water is pumped to the surface to be degassed with a gas extraction system. The large pumping rate may disturb the natural flow field and requires substantial field logistics. Hence, we propose a new in-situ degassing method, in which membrane contactors are used to degas the groundwater directly in the well and gas is collected at the surface. This way, field work is facilitated, groundwater system disturbance is minimized, and the gas sample is collected at a specific depth. We demonstrate the tightness of the system regarding atmospheric air contamination for a collection times of 24 h, which is sufficient for both low-level counting and laser-based counting methods for 85Kr. The minimal borehole diameter is 7.5 cm for the prototype presented in this research but can easily be reduced to smaller diameters. In a case study, we compare the results obtained with the new passive method with those from a conventional packer setup sampling. Additionally, 3H/3He samples were collected for both sampling regimes and the dating results were compared with those from 85Kr. A good agreement between tracer ages is demonstrated and the age stratigraphy is consistent with the expected age distribution for a porous unconfined aquifer. In addition, our study emphasizes the differences between the age information sampled with various methods. In conclusion, we demonstrate that the new in situ quasi-passive method provides a more representative age stratigraphy with depth in most cases.

Distributed temperature sensing is known to provide sharp signals which are very efficient for mapping hydraulically active fractures in wellbores. High-resolution temperature sensing has specifically demonstrated its capacity to characterize very low flows in wellbores. But as sharp as they can be, temperature profiles are often difficult to decipher. The aim of the present work is to provide and to test the “Borehole Heat Budget Calculator” (BHB Calculator), which is implemented as a fast and easy to use tool for the quantitative analysis of depth-temperature profiles. The Calculator is suitable for most pumping and draining configurations, as the heat budget is generalized for modelling multidirectional flow systems within the same wellbore. The formatted worksheet allows the quick exploitation of temperature logs, and is applicable for the characterization of distributed fractures in long screened wellbores. Objectives of the heat modelling are to enhance the readability of complex depth-temperature data, as well as to quantify distribution of inflow intensities and temperatures with depth. The use of heat budget helps to clearly visualize how heat conduction and heat advection contributions are distributed along wellbores profiles. Calculations of inflow temperatures and their evolution through pumping duration is a prerequisite to infer about the nature of aquifer properties (i.e. conduits, distributed or discrete fractures, porous media), as well as to give insight information about the mapping of effective flow paths draining the aquifer. The efficiency and limitations of the BHB Calculator are being tested through high-resolution temperature logging, along with complementary flowmetering and televiewing logging in fractured aquifers located in the St-Lawrence Lowlands, Quebec, Canada.

Interactions between lakes and groundwater are of increasing concern for freshwater environmental management but are often poorly characterized. Groundwater inflow to lakes, even at low rates, has proven to be a key in both lake nutrient balances and in determining lake vulnerability to pollution. Although difficult to measure using standard hydrometric methods, significant insight into groundwater–lake interactions has been acquired by studies applying geochemical tracers. However, the use of simple steady-state, well-mixed models, and the lack of characterization of lake spatiotemporal variability remain important sources of uncertainty, preventing the characterization of the entire lake hydrological cycle, particularly during ice-covered periods. In this study, a small groundwater-connected lake was monitored to determine the annual dynamics of the natural tracers, water stable isotopes and radon-222, through the implementation of a comprehensive sampling strategy. A multilayer mass balance model was found outperform a well-mixed, one-layer model in terms of quantifying groundwater fluxes and their temporal evolution, as well as characterizing vertical differences. Water stable isotopes and radon-222 were found to provide complementary information on the lake water budget. Radon-222 has a short response time, and highlights rapid and transient increases in groundwater inflow, but requires a thorough characterization of groundwater radon-222 activity. Water stable isotopes follow the hydrological cycle of the lake closely and highlight periods when the lake budget is dominated by evaporation versus groundwater inflow, but continuous monitoring of local meteorological parameters is required. Careful compilation of tracer evolution throughout the water column and over the entire year is also very informative. The developed models, which are suitable for detailed, site-specific studies, allow the quantification of groundwater inflow and internal dynamics during both ice-free and ice-covered periods, providing an improved tool for understanding the annual water cycle of lakes.

There is growing concern worldwide about the exposure of groundwater resources to pharmaceutically active compounds (PhACs) and agricultural contaminants, such as pesticides, nitrate, and Escherichia coli. For regions with a low population density and an abundance of water, regional contamination assessments are not carried out systematically due to the typically low concentrations and high costs of analyses. The objectives of this study were to evaluate regional-scale contaminant distributions in untreated groundwater in a rural region of Quebec (Canada). The geological and hydrogeological settings of this region are typical of post-glacial regions around the world, where groundwater flow can be complex due to heterogeneous geological conditions. A new spatially distributed Anthropogenic Footprint Index (AFI), based on land use data, was developed to assess surface pollution risks. The Hydrogeochemical Vulnerability Index (HVI) was computed to estimate aquifer vulnerability. Nine wells had detectable concentrations of one to four of the 13 tested PhACs, with a maximum concentration of 116ng·L-1 for benzafibrate. A total of 34 of the 47 tested pesticides were detected in concentrations equal to or greater than the detection limit, with a maximum total pesticide concentration of 692ng·L-1. Nitrate concentrations exceeded 1mg·L-1 N-NO3 in 15.3% of the wells, and the Canadian drinking water standard was exceeded in one well. Overall, 13.5% of the samples had detectable E. coli. Including regional-scale sources of pollutants to the assessment of aquifer vulnerability with the AFI did not lead to the identification of contaminated wells, due to the short groundwater flow paths between recharge and the sampled wells. Given the occurrence of contaminants, the public health concerns stemming from these new data on regional-scale PhAC and pesticide concentrations, and the local flow conditions observed in post-glacial terrains, there is a clear need to investigate the sources and behaviours of local-scale pollutants.

Rationale A method to measure the δ2 H and δ18 O composition of pore water in soil samples using direct vapour equilibration and laser spectrometry was first described in 2008, and was rapidly adopted. Here, we describe an improved setup to measure pore water δ2 H and δ18 O values through direct vapour equilibration with a laser spectrometer, combining a liquid and a vapour mode for water isotope analyses, and resulting in improved accuracy. Methods We first tested new gas sampling bags as part of the equilibration protocol. Then, to assess measurement accuracy, vapour samples from equilibrated liquid waters of known isotope composition were measured in the liquid mode of the analyser using the new setup as well as the manufacturer's vapour mode. Various modes of preparing liquid water standards, namely equilibration, nebulisation, and vapourisation, were tested to determine the best calibration in terms of accuracy. Finally, the proposed modified liquid setup was validated by analysing water vapour equilibrated from soil pore water of a known composition. Results The δ2 H and δ18 O measurements were found to be more accurate by the modified liquid mode than by the factory-setup vapour mode. The strong and non-linear dependence of measured δ2 H and δ18 O values on H2 O concentration in vapour mode, especially at concentrations equal to the vapour pressure saturation typically found in laboratories, is problematic for corrections. Regarding calibration and standards, the use of two equilibrated liquid water standards was found to best calibrate measurements in the modified liquid setup. Finally, the modified liquid mode setup and its calibration, as described here, were shown to be appropriate for soil pore water analysis. Conclusions The proposed modified setup results in more precise δ2 H and δ18 O soil pore water values than the usual protocols. An average standard deviation of 0.04‰ for δ18 O values and 0.3‰ for δ2 H values, based on 228 soil sample analyses, was obtained.

The oxygen isotope composition of dissolved inorganic phosphate (d18Op) offers new opportunities to understand the sources and the fate of phosphorus (P) in freshwater ecosystems. However, current analytical protocols for determining d18Op are unable to generate reliable data for samples in which ambient P concentrations are extremely low, precisely the systems in which d18Op may provide new and important insights into the biogeochemistry of P. In this paper, we report the development, testing and initial application of a new technique that enables d18Op analysis to be extended into such ecosystems. The Twist Spinning Mode (TSM) protocol described here enables >1000 L of sample with a P concentration

General and isotopic geochemistry of groundwater is an essential tool to decipher hydrogeological contexts and flow paths. Different hydrogeochemical patterns may result from the inherent physical aquifer heterogeneity, which may go unnoticed without detailed investigations gathered from multilevel or multiple observation wells. An alternative to overcome the frequent unavailability of multiple wellbores at sites is to perform a detailed investigation on the single wellbore available. In this perspective, the aim of this study is to use passive samplers to sequentially collect groundwater at depths in long–screened wellbores. Such investigation is carried out for major ions and stable isotopes compositions (δ2H, δ18O, δ13C) at ten sites in the context of fractured carbonate aquifers of the St. Lawrence Lowlands (Quebec, Canada). The information gathered from the calco–carbonic system, major ions and stable isotopes report poorly stratified and evolved groundwater bodies. Contribution of water impacted by anthropogenic activities, such as road salts pollution and carbon sources from C4 vegetation, when they occur, are even observed at the greatest depths. Such observations suggest quick flow paths and efficient mixing conditions, which leads to significant contributions of contemporary groundwater bodies in the fractured aquifers investigated down to depths of about 100 m. Although physical aquifer investigation reported few and heterogeneously distributed fractures per wellbore, hydrogeochemical findings point to at overall well interconnected fracture networks in the aquifer and high vulnerability of groundwater, even at significant depths.

The assessment of groundwater quality in shallow aquifers is of high societal relevance given that large populations depend directly on these water resources. The purpose of this study was to establish links between groundwater quality, groundwater residence times, and regional geology in the St. Lawrence Lowlands fractured bedrock aquifer. The study focuses on a 4500 km2 watershed located in the St. Lawrence Lowlands of the province of Quebec in eastern Canada. A total of 150 wells were sampled for major, minor, and trace ions. Tritium (3H) and its daughter element, 3He, as well as radiocarbon activity (A14C) were measured in a subset of wells to estimate groundwater residence times. Results show that groundwater evolves from a Ca–HCO3 water type in recharge zones (i.e., the Appalachian piedmont) to a Na–HCO3 water type downgradient, toward the St. Lawrence River. Locally, barium (Ba), fluoride (F), iron (Fe), and manganese (Mn) concentrations reach 90, 2, 18, and 5.9 mg/L respectively, all exceeding their respective Canadian drinking water limits of 1, 1.5, 0.3, and 0.05 mg/L. Release of these elements into groundwater is mainly controlled by the groundwater redox state and pH conditions, as well as by the geology and the duration of rock–water interactions. This evolution is accompanied by increasing 3H/3He ages, from 4.78 ± 0.44 years upgradient to more than 60 years downgradient. Discrepancies between calculated 3H/3He and 14C water ages (the latter ranging from 280 ± 56 to 17,050 ± 3410 years) suggest mixing between modern water and paleo-groundwater infiltrated through subglacial recharge when the Laurentide Ice Sheet covered the study area, and during the following deglaciation period. A linear relationship between 3H activity and corrected 14C versus Mg/Ca and Ba support a direct link between water residence time and the chemical evolution of these waters. The Ba, F, Fe, and Mn concentrations in groundwater originate from Paleozoic rocks from both the St. Lawrence Platform and the Appalachian Mountains. These elements have been brought to the surface by rising hydrothermal fluids along regional faults, and trapped in sediment during their deposition and diagenesis due to reactions with highly sulfurous and organic matter-rich water. Large-scale flow of meltwater during subglacial recharge and during the subsequent retreat of the Laurentide Ice Sheet might have contributed to the leaching of these deposits and their enrichment in the present aquifers. This study brings a new and original understanding of the St. Lawrence Lowlands groundwater system within the context of its geological evolution.

Bank filtration is a popular pre-treatment method to produce drinking water as it benefits from the natural capacity of the sediments to attenuate contaminants. Under flood conditions, bank filtration systems are known to be vulnerable to contamination, partly because flow patterns may evolve at short timescales and result in a rapid evolution of the origin and travel times of surface water in the aquifer. However, high frequency monitoring for water quality is not common practice yet, and water quality management decisions for the operation of bank filtration systems are typically based on weekly to monthly assays. The aim of this study is to illustrate how monitoring strategies of environmental tracers at flood-affected sites can be optimized and to demonstrate how tracer-based evidence can help to define adequate pumping strategies. Data acquisition spanned two intense flood events at a two-lake bank filtration site. Based on bacteriological indicators, the bank filtration system was shown to be resilient to the yearly recurring flood events but more vulnerable to contamination during the intense flood events. The origin of the bank filtrate gradually evolved from a mixture between the two lakes towards a contribution of floodwater and one lake only. Automatized measurements of temperature and electrical conductivity at observation wells allowed to detect changes in the groundwater flow patterns at a daily timescale, while the regulatory monthly monitoring for indicator bacteria did not fully capture the potential short timescale variability of the water quality. The recovery to pre-flood conditions was shown to be accelerated for the wells operating at high rates (i.e., ≥1000 m3/day), partly because of floodwater storage in the vicinity of the less active wells. These results establish new perspectives to anticipate water quality changes through selected pumping schemes, which depend on and must be adapted to site-specific water quality issues.

This paper presents the various tools and data sources in British Columbia (Canada) that can be used by environmental consultants to assess the potential of cross-contamination between shale gas formation fluids and shallow aquifers from hydraulic fracturing and related oil and gas activities. A systematic approach for evaluating the potential of cross-contamination using these data sources is applied to a specific case study at an undisclosed location in the northeastern part of the province. This approach includes defining and then evaluating the basic criteria for assessing the potential of cross-contamination. These criteria are: a leak source; a driving force such as buoyancy or head differential and a leakage pathway. This study has revealed that there is a potential of cross-contamination due to hydraulic fracturing activities and wellbore integrity issues. Wellbore integrity can be compromised by induced seismic events or by unintentional communication with offset hydraulic fractured wells. Induced seismicity is linked to the activity of hydraulic fracturing as well as to the deep disposal of wastewater.

Lakes are under increasing pressure due to widespread anthropogenic impacts related to rapid development and population growth. Accordingly, many lakes are currently undergoing a systematic decline in water quality. Recent studies have highlighted that global warming and the subsequent changes in water use may further exacerbate eutrophication in lakes. Lake evolution depends strongly on hydrologic balance, and therefore on groundwater connectivity. Groundwater also influences the sensitivity of lacustrine ecosystems to climate and environmental changes, and governs their resilience. Improved characterization of groundwater exchange with lakes is needed today for lake preservation, lake restoration, and sustainable management of lake water quality into the future. In this context, the aim of the present paper is to determine if the future evolution of the climate, the population, and the recharge could modify the geochemistry of lakes (mainly isotopic signature and quality via phosphorous load) and if the isotopic monitoring of lakes could be an efficient tool to highlight the variability of the water budget and quality. Small groundwater-connected lakes were chosen to simulate changes in water balance and water quality expected under future climate change scenarios, namely representative concentration pathways (RCPs) 4.5 and 8.5. Contemporary baseline conditions, including isotope mass balance and geochemical characteristics, were determined through an intensive field-based research program prior to the simulations. Results highlight that future lake geochemistry and isotopic composition trends will depend on four main parameters: location (and therefore climate conditions), lake catchment size (which impacts the intensity of the flux change), lake volume (which impacts the range of variation), and lake G index (i.e., the percentage of groundwater that makes up total lake inflows), the latter being the dominant control on water balance conditions, as revealed by the sensitivity of lake isotopic composition. Based on these model simulations, stable isotopes appear to be especially useful for detecting changes in recharge to lakes with a G index of between 50 and 80 %, but response is non-linear. Simulated monthly trends reveal that evolution of annual lake isotopic composition can be dampened by opposing monthly recharge fluctuations. It is also shown that changes in water quality in groundwater-connected lakes depend significantly on lake location and on the intensity of recharge change.

International audience; This study attempts to place constraints on groundwater residence times using helium isotopes and 14C of a regional groundwater flow system – the Becancour River watershed – located midway between Montreal and Quebec City (Quebec, Canada). This densely populated region is one of the main targets for shale gas exploitation in Eastern Canada. For this reason, this watershed has been the focus of a detailed aquifer study to gain a better understanding of groundwater resources, both in terms of availability and quality. In the current study, noble gases were sampled and analyzed in twenty-eight wells from a Quaternary granular aquifer and a regional bedrock aquifer of Ordovician age. Tritium (3H) and radiocarbon (A14C) activities were measured on selected wells. Helium isotopic ratios 3He/4He (R) normalized to that of the atmosphere (Ra = 1.386 × 10− 6) range from R/Ra = 0.039 ± 0.003 to 3.109 ± 0.065. The helium isotopic signatures point to the presence of three water bodies: 1) modern infiltration water with nearly atmospheric helium isotopic ratio and little post-bomb tritium recharging the shallower granular aquifer; 2) mid-50s tritium-rich water slightly mineralized; and 3) an older water component rich in terrigenic helium flowing in from the bedrock fractured aquifer. Uncorrected 14C ages range from 15 ka to modern. 14C is affected by several dead carbon reservoirs related to carbonate dissolution, cations exchange, oxidation of organic matter and methanogenesis. Adjusted 14C ages calculated with NETPATH range from 7 ka to modern. Older 14C ages correspond to the end of the regional re-organization of the hydrological system following deglaciation and isostatic rebound. Noble gas recharge paleotemperatures are 4–9 °C colder than the present temperatures, although no clear relation with ages has been found. The relationship between the helium isotopic ratios and 14C ages suggests that the regional bedrock aquifer is affected by mixing between these three water sources. Calculated (U–Th)/4He ages can be partially explained by in situ production of 4He in the aquifer rock and the addition of a radiogenic helium source external to the aquifer. Calculated minimum helium fluxes of 1.0 × 10− 8 to 1.8 × 10− 7 cm3 STP cm− 2 yr− 1 are tens to hundreds of times lower than the average continental crust flux of 3.3 × 10− 6 cm3 STP cm− 2 yr− 1, suggesting local sources, possibly from production of radiogenic helium in the shale gas formations underlying the studied aquifers. The occurrence of old groundwater in this aquifer system clearly limits the renewable resource and increases the risk of overexploitation in the case of increased use or in the case of pollution from different sources.

International audience; Iron is known to stimulate surface ocean productivity, as well as intervene with bacterially-mediated processes of organic matter remineralization, during early diagenesis. In this paper, we examine the influence of iron supply on the geochemistry (trace metals, δ34S, organic matter) of sedimentary rocks deposited in a clastic-dominated marine ramp environment. To this end, we studied two Late Jurassic formations of the Boulonnais area (North-France). Both formations were deposited under quite similar conditions, but they differ in the reactive-iron supply they received. Only one of the two formations was affected by the particulate iron shuttle process. Our results indicate that 1)the iron shuttle may be recorded through concomitant enrichments in P, Mo, As and Sb; 2)a limited reactive-iron supply will allow the sulfurization of organic matter, even in a context of moderate productivity. Thus sulfurization can be a factor favoring a noticeable accumulation of organic matter: iron may thus be an important agent in the C cycle.

A reliable estimate of recharge is needed for the sustainable management of groundwater resources. Water stable isotope (delta O-18 and delta H-2) profiles in the unsaturated zone are frequently used to quantify groundwater recharge based on the seasonality of water isotopic compositions in precipitation. A very simple approach consists of integrating the soil water content between peak values of soil water isotopic composition, typically corresponding to precipitation signatures from warm and cold seasons. When precipitation isotopic compositions are available, a conceptual surface water isotopes budget and lumped parameter dispersion model can be computed. These models were applied on two field sites with similar permeable soils with grass cover but contrasting recharge regimes and seasonality, one in the Paris Basin (France) with continuous recharge from autumn to spring and the other in the St. Lawrence Lowlands (Quebec, Canada) with episodic recharge in fall and after snowmelt. For the two sites, the peak-to-peak method and isotope surface budget led to comparable recharge intensities. At least at the Paris Basin site, evaporation was shown to slightly modify the average unsaturated zone and hence groundwater isotope composition. The proposed parameterization of isotope fractionation due to evaporation allows qualitative estimation of the fraction of evaporation, at least during the recharge seasons. In spite of its simplifications and limitations, the proposed parsimonious model can give estimates of recharge in a variety of sites even if they are not well characterized, as it benefits from the large availability of monthly isotopic compositions in precipitation.

International audience; This work aims to provide an overview of the thermal processes that shape wellbore temperature profiles under static and dynamicconditions. Understanding of the respective influences of advection and conduction heat fluxes is improved through the useof a new heat budget at the borehole scale. Keeping in mind the thermal processes involved, a qualitative interpretation of thetemperature profiles allows the occurrence, the position, and the origin of groundwater flowing into wellbores from hydraulicallyactive fractures to be constrained.With the use of a heat budget developed at the borehole scale, temperature logging efficiency hasbeen quantitatively enhanced and allows inflow temperatures to be calculated through the simultaneous use of a flowmeter. Undercertain hydraulic or pumping conditions, both inflow intensities and associated temperatures can also be directly modelled fromtemperature data and the use of the heat budget. Theoretical and applied examples of the heat budget application are provided.Applied examples are shown using high-resolution temperature logging, spinner flow metering, and televiewing for three wellsinstalled in fractured bedrock aquifers in the St-Lawrence Lowlands, Quebec, Canada. Through relatively rapid manipulations,thermal measurements in such cases can be used to detect the intervals or discrete positions of hydraulically active fractures inwellbores, as well as the existence of ambient flows with a high degree of sensitivity, even at very low flows. Heat budget calculationsat the borehole scale during pumping indicate that heat advection fluxes rapidly dominate over heat conduction fluxes with theborehole wall. The full characterization of inflow intensities provides information about the distribution of hydraulic propertieswith depth. The full knowledge of inflow temperatures indicates horizons that are drained from within the aquifer, providingadvantageous information on the depth from which groundwater originates during pumping.1. Introduction

In regions where aquifers sustain rivers, the location and quantification of groundwater discharge to surface water are important to prevent pollution hazards, to quantify and predict low flows and to manage water supplies. 222Rn is commonly used to determine groundwater discharge to rivers. However, using this isotopic tracer is challenging because of the high diffusion capacity of 222Rn in open water. This study illustrates how a combination of isotopic tracers can contribute to an enhanced understanding of groundwater discharge patterns in small rivers. The aim of this paper is to combine 222Rn and δ13CDIC to better constrain the physical parameters related to the degassing process of these tracers in rivers. The Hallue River (northern France) was targeted for this study because it is sustained almost exclusively by a fractured chalk aquifer. The isotopes 222Rn, δ13CDIC, δ2H and δ18O were analysed along with other natural geochemical tracers. A mass balance model was used to simulate 222Rn and δ13CDIC. The results of δ2H and δ18O analyses prove that evaporation did not occur in the river. The calibration of a numerical model to reproduce 222Rn and δ13CDIC provides a best-fit diffusive layer thickness of 3.21 × 10−5 m. This approach is particularly useful for small rivers flowing over carbonate aquifers with high groundwater DIC where the evolution of river DIC reflects the competing processes of groundwater inflow and CO2 degassing. This approach provides a means to evaluate groundwater discharge in small ungauged rivers. Copyright © 2014 John Wiley & Sons, Ltd.

At many bank filtration (BF) sites, mixing ratios between the contributing sources of water are typically regarded as values with no temporal variation, even though hydraulic conditions and pumping regimes can be transient. This study illustrates how anthropic and meteorological forcings influence the origin of the water of a BF system that interacts with two lakes (named A and B). The development of a time-varying binary mixing model based on electrical conductivity (EC) allowed the estimation of mixing ratios over a year. A sensitivity analysis quantified the importance of considering the temporal variability of the end-members for reliable results. The model revealed that the contribution from Lake A may vary from 0% to 100%. At the wells that were operated continuously at &gt, 1000 m3/day, the contribution from Lake A stabilized between 54% and 78%. On the other hand, intermittent and occasional pumping regimes caused the mixing ratios to be controlled by indirect anthropic and/or meteorological forcing. The flow conditions have implications for the quality of the bank filtrate, as highlighted via the spatiotemporal variability of total Fe and Mn concentrations. We therefore propose guidelines for rapid decision-making regarding the origin and quality of the pumped drinking water.

International audience; 222)Rn has been increasingly used to identify groundwater contribution to surface water. Particular attention has been paid to analytical protocols and counting parameters used for liquid alpha scintillation measurements over a range of activities covering river and groundwater domains. Direct measurements and Rn-extraction protocols are optimized, and scintillometer efficiency is calibrated using international standards over the 0.5-35Bq/L range. The interval of activities was performed in surface water and groundwater from a small Canadian watershed. Copyright 2013. Published by Elsevier Ltd.

The development of intense agriculture in semiarid areas modifies intensity and spatial distribution of groundwater recharge by summing irrigation return flow to limited rainfall infiltration. Environmental tracers provide key information, but their interpretation is complicated by more complex groundwater flow patterns. In multilayered aquifers, the real origin of the groundwater samples is hard to assess because of local mixing processes occurring inside long-screened boreholes. We use environmental tracers (14C, 13C, 2H, 18O, 3H) to investigate the long-term evolution of recharge in the five-layer Campo de Cartagena aquifer in South-Eastern Spain, in addition to high-resolution temperature loggings to identify the depth of origin of groundwater. Despite the complex background, this methodology allowed a reliable interpretation of the geochemistry and provided a better understanding of the groundwater flow patterns. The tritium method did not give good quantitative results because of the high variability of the recharge signal but remained an excellent indicator of recent recharge. Nonetheless, both pre-anthropization and post-anthropization recharge regime could be identified and quantified by radiocarbon. Before the development of agriculture, recharge varied from 17 mm.year-1 at the mountain ranges to 6 mm.year-1 in the plain, whereas the mean annual rainfall is about 300 mm. In response to the increase of agricultural activity, recharge fluxes to the plain were amplified and nowadays reach up to 210 mm.year-1 in irrigated areas. These values are strengthened by global water budget and local unsaturated zone studies. Copyright © 2013 John Wiley & Sons, Ltd.

Given increasing anthropogenic and climatic pressures on water resources, groundwater and surface water need to be better managed and preserved. As these two water stocks can be connected to each other, their evolutions are linked and need to be considered as such. However, interactions between lakes and groundwater are not well understood and, most of the time, are not taken into account. Therefore, establishing a comprehensive approach to quantify groundwater and lakes’ hydrogeochemical interactions in various settings is of foremost importance for assessing the sensitivity of lakes to groundwater evolution. In this study, small kettle lakes set in fluvioglacial deposits and that are most likely well connected to shallow unconfined aquifers are specifically targeted. Geochemistry and isotopic results highlight that groundwater flux to the lakes is generally the dominant parameter of the lake water budget. The 222Rn results in particular suggest that 38% of the studied lakes have a high proportion of groundwater in their balances. It appears that the different tracers are complementary: geochemistry is influenced by groundwater inflows, reflecting its quality and the local geology, whereas water stable isotopes correspond directly to the volumetric lake water budget, and both of these tracers are impacted by in-lake processes. Moreover, the third tracer considered, 222Rn, highlights the location of groundwater inputs in space and time. Finally, the studied kettle lakes are characterized by a short to medium flushing time by groundwater. As a result, these lakes can be highly sensitive to environmental and climate changes affecting groundwater.

Radiocarbon decay is rarely used to assess the residence time of modern groundwater due to the low resolution of its long half-life in comparison to the expected range of ages. Nonetheless, the modern 14C peak induced by the nuclear bomb tests traces efficiently the impacts of recent human activities on groundwater recharge, as well as for tritium. A simple lumped parameter model (LPM) was implemented in order to assess the interest of 14C and 3H nuclear peaks in a highly anthropized aquifer system of southeastern Spain under intense agricultural development. It required i) to assess a correction factor for modern 14C activities and ii) to reconstruct the 3H recharge input function, affected by irrigation. In such a complex hydrogeological context, an exponential model did not provide satisfying results for all samples. A better solution was reached by taking into account the qualitative recent variation of the recharge rates into a combined exponential flow and piston flow model. Apart from presenting an uncommon approach for 14C dating of modern groundwater, this study highlights the need of considering not only the variation of the tracer but also the variability of recharge rates in LPMs.

14C dating of groundwater depends on the isotopic composition of both the solid carbonate and the soil CO2 and requires the use of 14C age correction models. To better assess the variability of the 14C activity of soil CO2 (A14Csoil-CO2) and the δ13C of soil CO2 (δ13Csoil-CO2), which are two parameters used in 14C age correction models, we studied the different processes involving carbon isotopes in the soil. The approach used experimental data from two sites in France (Fontainebleau sands and Astian sands) and a steady-state transport model. In most cases, the 14C activity (A14C) of atmospheric CO2 is directly used in the 14C age correction models as the A14Csoil-CO2. However, we demonstrate that since 1950, the evolution of the A14Csoil-CO2 reflects the competition between the fluxes of root-derived CO2 and organic matter-derived CO2. Therefore, the A14Csoil-CO2 must be used to date groundwater that is younger than 60 years old. Moreover, the δ13C of soil CO2 (δ13Csoil-CO2) showed large seasonal variations that must be taken into account in selecting the δ13Csoil-CO2 for 14C age correction models.

14C dating models are limited when considering recent groundwater for which the carbon isotopic signature of the total dissolved inorganic carbon (TDIC) is mainly acquired in the unsaturated zone. Reducing the uncertainties of dating thus implies a better identification of the processes controlling the carbon isotopic composition of the TDIC during groundwater recharge. Geochemical interactions between gas, water and carbonates in the unsaturated zone were investigated for two aquifers (the carbonate-free Fontainebleau sands and carbonate-bearing Astian sands, France) in order to identify the respective roles of CO2 and carbonates on the carbon isotopic signatures of the TDIC; this analysis is usually approached using open or closed system terms. Under fully open system conditions, the seasonality of the 13C values in the soil CO2 can lead to important uncertainties regarding the so-called “initial 14C activity” used in 14C correction models. In a carbonate-bearing unsaturated zone such as in the Astian aquifer, we show that an approach based on fully open or closed system conditions is not appropriate. Although the chemical saturation between water and calcite occurs rapidly within the first metre of the unsaturated zone, the carbon isotopic contents (δ13C) of the CO2 and the TDIC evolve downward, impacted by the dissolution–precipitation of the carbonates. In this study, we propose a numerical approach to describe this evolution. The δ13C and the A14C (radiocarbon activity) of the TDIC at the base of the carbonate-bearing unsaturated zone depends on (i) the δ13C and the A14C of the TDIC in the soil determined by the soil CO2, (ii) the water’s residence time in the unsaturated zone and (iii) the carbonate precipitation–dissolution fluxes. In this type of situation, the carbonate δ13C–A14C evolutions indicate the presence of secondary calcite and permit the calculation of its accretion flux, equal to ∼4.5±0.5×10-9molgrock-1yr-1. More generally, for other sites under temperate climate and with similar properties to the Astian sands site, this approach allows for a reliable determination of the carbon isotopic composition at the base of the unsaturated zone as the indispensable “input function” data of the carbon cycle into the aquifer.

International audience; Karst aquifers are characterized by a strong heterogeneity in their physical properties. The purpose of the study is the spatial variability of water transfers in a carbonated karstic aquifer. To this end, a high spatial density of information about the water transfer is needed. The characteristics of the site, a topographic hill of 13 km2 with eight boreholes, which was monitored hourly over four years, allows the study of the spatial variability of water transfers. The variability of the impulse response of the system is studied using autocorrelation and cross-correlation analysis between the rainfall and piezometric level time series. The shapes of the autocorrelation and cross-correlation functions vary according to the geographical location of the boreholes, that proves a spatial organization of the groundwater transfer. The response time varies depending on the thickness of the unsaturated zone by an unusual inverse correlation. In this case, the water level signal spatially integrates the signal transfer of the unsaturated zone and the signal transfer of the saturated part of the aquifer. Consequently, inertia and response time increased with the distance between the borehole and the top of piezometric dome. This description supports highly organized fast transfers in this karst aquifer and a highly connected fracture network.

International audience; Groundwater vulnerability mapping provides useful but limited information for developing protection plans of the resource. Classical vulnerability ranking methods often do not take into account complex hydrostratigraphy and never consider groundwater flow dynamics. The objective of this work was to test the potential of major ion chemistry to assess regional-scale intrinsic groundwater vulnerability. Because it reflects water–sediment and water–rock interactions, the new vulnerability index reflects both infiltration processes and groundwater hydrodynamics. The method was applied on a regional fractured bedrock aquifer located in the Becancour region of southern Quebec (Canada). In this region, hydrogeochemistry shows that freshly recharged groundwater evolves from (Ca, Mg)–HCO3 and Ca–SO4 to Na–HCO3 type with gradually increasing confinement conditions in the fractured aquifer and tends to Na–Cl type locally by mixing with trapped marine pore-water. The new method identified recharge areas as those of the highest vulnerability and gradually decreasing vulnerability as confinement of the aquifer increased. It also highlights local discontinuities in confinement that differ from the regional pattern. Results showed a good correlation between groundwater vulnerability estimated with the new method and nitrate occurrence in groundwater. Eighty-two per cent of all samples presenting detectable nitrate concentrations were characterized by a Hydrogeochemical Vulnerability Index greater than 9 (maximum is 10). The ability of the new vulnerability method to identify areas vulnerable to detectable nitrate concentrations was much higher than that deriving from the DRASTIC method. This work confirms that major ions chemistry contains significant information about groundwater vulnerability and could be used to improve groundwater resource management.

International audience; The release of radioactive iodine into geological media from nuclear waste disposal is an issue that has tobe considered since iodine is a biophilic element. 129I is, with 99Tc, one of the two long-lived radionuclidesthat have the highest mobility in radioactive waste disposal. Within this context, iodide retardation is stilla matter of debate. A low value of the retardation factor is generally accepted in soils without organicmatter, but the possibility for sorption cannot be completely ruled out. Since isotopic exchange with naturallyoccurring iodine is one of the main potential sorption mechanisms, site-specific retention parametersare needed. In the present paper, we study iodide transport in a sandy aquifer. A hydrogeologicalmodel was built to fit deuterium, bromide and iodide breakthrough data from in situ tracer test experiments.Within the precision range of the fitting, iodide is excluded from 2.5% of the effective porosity byanionic exclusion and presents a field retention factor (Kd) lower than 0.025 L/kg.

Introduction. - In the Nord-Pas-de-Calais region (northern France), the mining activity linked to the coal extraction resulted in the existence of many mine spoils. Most of the time, the choice of the mine spoil location has been made without knowing the potential contamination of the aquifers contained in the underlying formations by substances which can be solubilized and released in relation with the weathering of these mine spoils. The aim of this study is to determine the possible role of the mine spoils in the sulfate mineralization of the chalk aquifer. Previous works [Bernard, 1979; Droz, 1985] allow to consider several possible sources of sulfate in the coal basin: the dissolution of evaporitic minerals present in the Carboniferous limestones Formation which can locally contaminate per ascensum the chalk aquifer; the dissolution of gypsum contained in the Tertiary formations (Argiles de Louvil, Sables d'Ostricourt); sulfates of anthropic origin linked to the waste water discharge and/or to the agricultural practices; finally, the weathering of mine spoils which leads to the oxydation of the pyrite contained in the Carboniferous shales, and can release sulfate ions that may be transferred to the aquifer. Two sites have been selected 30 km to the south of Lille: site 1 lies directly on the Senonian-Turonian chalk while site 2 lies on the sandy-clayey Tertiary formations overlying the chalk formations (fig. 1-3). Geology and hydrogeology. - The waters have been sampled within the chalk aquifer (fig. 2). This water table forms the main resource in drinking water, currently exploited. The chalk aquifer is a free water table except where the Tertiary formations make this water table confined, as is the case for site 2. The recharge of the chalk aquifer is made by the percolation of the impluvium through the microporosity of the chalk with an infiltration velocity of 0.5 to 0.7 m per year [Vachier et al., 1979]. The chalk aquifer flow is schematically SW-NE to the Orchies basin (fig. 1). This flow is caused by the piezometric depression in the Orchies basin linked to industrial pumpage. Since the decrease of these pumpages, we can observe a rise of the chalk aquifer piezometric level evaluated to 10 m in the studied area. Material and methods. - Rock samples have been collected on the surface of the two sites and below it at site 1. Mineralogical analyses have been carried out on the bulk fraction as on the clayey fraction, the elementary analysis of total carbon and total sulphur has also been performed. Two water sampling surveys have been carried out on 19 sites. Sampling has been made from piezometers which reach the chalk aquifer and that are placed close to the mine spoils but also in a radius of 5 to 10 km around. Chemical and isotopic analyses have been made on the waters sampled at hydraulic upstream and dowstream of the mine spoils. In situ measurements have been carried out during the sampling. Piezometric levels have been taken at all the sampling sites. Results and discussion. - The carbon and sulphur contents have shown a superficial leaching of these elements on the mine spoils (fig. 9). The use of isotopic geochemistry and in particular the sulphur isotopes as tracers of the sulfate origin has permitted to identify two contribution sources at the two sites: a "mine spoil" source with a delta 34 S weakly negative (delta 34 S = -2,8 per mil, -3,9 per mil) which corresponds to the oxidation of sulfides contained by the Carboniferous shales and another source (delta 34 S = -20 per mil) corresponding to the gypsum of the "Sables d'Ostricourt" which is present only at site 2 (fig. 7, 10 & 11). This study has revealed the different behaviour of the two sites: for site 1, with a free water-table zone, the mine spoil leaching carries sulfate ions directly to the table whereas in the second site, with a confined aquifer zone, a part of the sulfate ions are reduced once exported to the table (the redox potential presents negative values; fig. 6). This bacterial reduction is made possible by the organic carbon leaching concomitant to the sulphur leaching on the mine spoils. This carbon contribution has been confirmed by the 14 C activity analysis: 14 C activity is characteristic of the chalk aquifer waters at the upstream of the mine spoil and noticeably lower downstream, this decrease can be linked to the "dead carbon" supply from the mine spoils (fig. 8). This organic carbon is involved in bacterially-mediated sulfate reduction (2CH 2 O + SO 4 (super 2-) --> 2HSO 3 (super -) + H (super +) + HS (super -) ). Conclusion. - Both studied mine spoils release sulfate ions to the Chalk aquifer, in response to the weathering and leaching of their surficial part. Using an isotope study-grounded approach, the influence of the mine spoils upon the sulfate enrichment of the water table can be distinguished from that of Cenozoic formations sometimes present between the chalk aquifer and the mine spoil basis. No other sulfate source seems to be involved in the studied area. Together with sulfate ions, the mine spoils export dissolved organic carbon. Both chemical species sustain bacterial activity (sulfate reducers) that develops where the water table is made confined by overlying, almost impervious, Cenozoic deposits. In that case, reducing conditions in the aquifer decrease the amount of sulfate ions present. Thus the simultaneous supply of sulfate and carbon by the mine spoils leads to a self-purification process where the aquifer is confined.

This paper describes the geochemical evolution of groundwater in the Bathonian and Bajocian aquifer along its flowpath. Since this aquifer represents one of the main sources of fresh water supply in the Caen area and has been subjected to a Holocene marine intrusion, its management requires a sound knowledge of (1) the primary conditions and (2) the potential influence of either natural or anthropogenic pressures. Groundwater vertical sampling validity is discussed with the contribution of high resolution temperature logging. The main processes of geochemical evolution along a groundwater flow line and the sea-water intrusion characteristics are discussed using ionic concentrations (Br − , F − and major elements) and isotopes (water δ 2 H and δ 18 O, TDIC δ 13 C and A 14 C, sulphate δ 18 O and δ 34 S). As the 13 C content of TDIC is used as a tracer of water-rock interaction, it shows evidence of specific chemical and isotopic evolutions of groundwater within the aquifer, both related to water-rock interaction and mineral equilibria in groundwater. All the above-mentioned tracers evolve downflow: cation concentrations are modified by exchange with clay minerals allowing a high F − concentration in groundwater, whereas Br − and SO 2− 4 concentrations appear to be redox condition dependant. Superimposed on these geochemical patterns, δ 18 O and δ 2 H compositions indicate that aquifer recharge has varied significantly through time. The chemical evolution of groundwater is locally affected by a salty water intrusion that is characterised by mixing between Flandrian fresh water and sea-water which has interacted with peat as evidenced by a high Br − /Cl − ratio and SO 2− 4 reduction.

We studied a 12.6-m-long sequence from Lake Abiyata (Central Ethiopia) to establish a reliable and accurate chronology for use in global paleoclimatic reconstructions. The 26 accelerator mass spectrometry radiocarbon (AMS 14C) ages, performed on carbonates and organic matter, define 2 parallel chronologies, representing the complete Holocene period. However, these chronologies show a significant discrepancy from 500 to 900 BP in depth; ages obtained on carbonates were always older than those on organic matter. The hydrogeological and geochemical behavior of the Lake Abiyata basin has shed light on this discrepancy. We found that the carbonate crystallization is due mainly to the mixing of lake waters with groundwaters from the multi-layered aquifer contained in the 600-m-thick basement of the lake. The 14C activity of total dissolved inorganic carbon (TDIC) measured by AMS from bottom and surface lake waters (111.4 and 111.8 pMC, respectively) confirms that the mixing occurs at the water-sediment interface. This evidence of groundwater participation in the carbonate crystallization calls into question the current paleoclimatic reconstructions based on inorganic carbonates in lakes. Specific attention should thus be given to the respective proportions of each end-member in the mixing for the quantitative estimation of the groundwater input. This will help to validate the paleoenvironmental reconstructions and to highlight an eventual diagenetical evolution of inorganic carbonates during burial, via the study of pore waters.