Florent Barbecot

Hydrochemical and isotopic characterisation of the Bathonian and Bajocian coastal aquifer of the Caen area (northern France)

Abstract 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.

Impact of climate changes during the last 5 million years on groundwater in basement aquifers

Climate change is thought to have major effects on groundwater resources. There is however a limited knowledge of the impacts of past climate changes such as warm or glacial periods on groundwater although marine or glacial fluids may have circulated in basements during these periods. Geochemical investigations of groundwater at shallow depth (80–400 m) in the Armorican basement (western France) revealed three major phases of evolution: (1) Mio-Pliocene transgressions led to marine water introduction in the whole rock porosity through density and then diffusion processes, (2) intensive and rapid recharge after the glacial maximum down to several hundred meters depths, (3) a present-day regime of groundwater circulation limited to shallow depth. This work identifies important constraints regarding the mechanisms responsible for both marine and glacial fluid migrations and their preservation within a basement. It defines the first clear time scales of these processes and thus provides a unique case for understanding the effects of climate changes on hydrogeology in basements. It reveals that glacial water is supplied in significant amounts to deep aquifers even in permafrosted zones. It also emphasizes the vulnerability of modern groundwater hydrosystems to climate change as groundwater active aquifers is restricted to shallow depths.

Comparing carbonate and organic AMS- (super 14) C ages in Lake Abiyata sediments (Ethiopia); hydrochemistry and paleoenvironmental implications.

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 (super 14) C) 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 ground-waters from the multi-layered aquifer contained in the 600-m-thick basement of the lake. The (super 14) C 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.

The potential of major ion chemistry to assess groundwater vulnerability of a regional aquifer in southern Quebec (Canada)

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.

Full range determination of 222Rn at the watershed scale by liquid scintillation counting

(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 0.5-35 Bq/L range. The interval of activities was performed in surface water and groundwater from a small Canadian watershed.

Geochemical and isotopic mass balances of kettle lakes in southern Quebec (Canada) as tools to document variations in groundwater quantity and quality

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.

Regional assessment of concentrations and sources of pharmaceutically active compounds, pesticides, nitrate, and E. coli in post-glacial aquifer environments (Canada)

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.

Interactions between groundwater and seasonally ice-covered lakes: using water stable isotopes and radon-222 multi-layer mass balance models

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.

Identification et caractérisation d'un biseau salin dans l'aquifère côtier du Bajocien-Bathonien de la région de Caen (France)*

Abstract 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.

High-Resolution Wellbore Temperature Logging Combined with a Borehole-Scale Heat Budget: Conceptual and Analytical Approaches to Characterize Hydraulically Active Fractures and Groundwater Origin

This work aims to provide an overview of the thermal processes that shape wellbore temperature profiles under static and dynamic conditions. Understanding of the respective influences of advection and conduction heat fluxes is improved through the use of a new heat budget at the borehole scale. Keeping in mind the thermal processes involved, a qualitative interpretation of the temperature profiles allows the occurrence, the position, and the origin of groundwater flowing into wellbores from hydraulically active fractures to be constrained. With the use of a heat budget developed at the borehole scale, temperature logging efficiency has been quantitatively enhanced and allows inflow temperatures to be calculated through the simultaneous use of a flowmeter. Under certain hydraulic or pumping conditions, both inflow intensities and associated temperatures can also be directly modelled from temperature 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 wells installed 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 in wellbores, as well as the existence of ambient flows with a high degree of sensitivity, even at very low flows. Heat budget calculations at the borehole scale during pumping indicate that heat advection fluxes rapidly dominate over heat conduction fluxes with the borehole wall. The full characterization of inflow intensities provides information about the distribution of hydraulic properties with depth. The full knowledge of inflow temperatures indicates horizons that are drained from within the aquifer, providing advantageous information on the depth from which groundwater originates during pumping.