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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.

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

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.

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.

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.

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.

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.

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.

The Bajocian-Bathonian aquifier in the Caen region is largely exploited for drinking water and agriculture. When this coastal carbonated aquifer becomes confined, groundwater presents an increasing TDS both vertically and along the flow path. This is explained by water-carbonate interaction and by a mixing with marine water (up to 4 %). Radiocarbon dating, after correction of the initial activity according to different models, shows a wide range of groundwater ‘ages’, from 40 000 years B.P. to the present. The marine transgression has thus been estimated as having occurred during the Early Holocene period.