Virginie Vergnaud-Ayraud

Nitrate dynamics in agricultural catchments deduced from groundwater dating and long-term nitrate monitoring in surface- and groundwaters

Although nitrate export in agricultural catchments has been simulated using various types of models, the role of groundwater in nitrate dynamics has rarely been fully taken into account. We used groundwater dating methods (CFC analyses) to reconstruct the original nitrate concentrations in the groundwater recharge in Brittany (Western France) from 1950 to 2009. This revealed a sharp increase in nitrate concentrations from 1977 to 1990 followed by a slight decrease. The recharge concentration curve was then compared with past chronicles of groundwater concentration. Groundwater can be interpreted as resulting from the annual dilution of recharge water in an uncontaminated aquifer. Two aquifers were considered: the weathered aquifer and the deeper fractured aquifer. The nitrate concentrations observed in the upper part of the weathered aquifer implied an annual renewal rate of 27 to 33% of the reservoir volume while those in the lower part indicated an annual renewal rate of 2-3%. The concentrations in the deep fractured aquifer showed an annual renewal rate of 0.1%. The river concentration can be simulated by combining these various groundwater reservoirs with the recharge. Winter and summer waters contain i) recharge water, or water from the variably saturated zone with rapid transfer and high nitrate concentrations, and ii) a large contribution (from 35 to 80% in winter and summer, respectively) from the lower part of the aquifer (lower weathered aquifer and deep fractured aquifer). This induces not only a relatively rapid response of the catchment to variations in agricultural pressure, but also a potential inertia which has to be taken into account.

Groundwater Isolation Governs Chemistry and Microbial Community Structure along Hydrologic Flowpaths

This study deals with the effects of hydrodynamic functioning of hard-rock aquifers on microbial communities. In hard-rock aquifers, the heterogeneous hydrologic circulation strongly constrains groundwater residence time, hydrochemistry, and nutrient supply. Here, residence time and a wide range of environmental factors were used to test the influence of groundwater circulation on active microbial community composition, assessed by high throughput sequencing of 16S rRNA. Groundwater of different ages was sampled along hydrogeologic paths or loops, in three contrasting hard-rock aquifers in Brittany (France). Microbial community composition was driven by groundwater residence time and hydrogeologic loop position. In recent groundwater, in the upper section of the aquifers or in their recharge zone, surface water inputs caused high nitrate concentration and the predominance of putative denitrifiers. Although denitrification does not seem to fully decrease nitrate concentrations due to low dissolved organic carbon concentrations, nitrate input has a major effect on microbial communities. The occurrence of taxa possibly associated with the application of organic fertilizers was also noticed. In ancient isolated groundwater, an ecosystem based on Fe(II)/Fe(III) and S/SO4 redox cycling was observed down to several 100 of meters below the surface. In this depth section, microbial communities were dominated by iron oxidizing bacteria belonging to Gallionellaceae. The latter were associated to old groundwater with high Fe concentrations mixed to a small but not null percentage of recent groundwater inducing oxygen concentrations below 2.5 mg/L. These two types of microbial community were observed in the three sites, independently of site geology and aquifer geometry, indicating hydrogeologic circulation exercises a major control on microbial communities.

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.

Strontium isotopes as tracers of water-rocks interactions, mixing processes and residence time indicator of groundwater within the granite-carbonate coastal aquifer of Bonifacio (Corsica, France)

This study aims at identifying the water-rock interactions and mixing rates within a complex granite-carbonate coastal aquifer under high touristic pressure. Investigations have been carried out within the coastal aquifer of Bonifacio (southern Corsica, France) mainly composed of continental granitic weathering products and marine calcarenite sediments filling a granitic depression. A multi-tracer approach combining physico-chemical parameters, major ions, selected trace elements, stable isotopes of the water molecule and 87Sr/86Sr ratios measurements is undertaken for 20 groundwater samples during the low water period in November 2014. 5 rock samples of the sedimentary deposits and surrounding granites are also analysed. First, the water-rock interactions processes governing the groundwater mineralization are described in order to fix the hydrogeochemical background. Secondly, the flow conditions are refined through the quantification of inter aquifer levels mixing, and thirdly, the kinetics of water-rock interaction based on groundwater residence time from a previous study using CFCs and SF6 are quantified for the two main flow lines. A regional contrast in the groundwater recharge altitude allowed the oxygene-18 to be useful combined with the 87Sr/86Sr ratios to differentiate the groundwater origins and to compute the mixing rates, revealing the real extension of the watershed and the availability of the resource. The results also highlight a very good correlation between the groundwater residence time and the spatial evolution of 87Sr/86Sr ratios, allowing water-rock interaction kinetics to be defined empirically for the two main flow lines through the calcarenites. These results demonstrate the efficiency of strontium isotopes as tracers of water-rock interaction kinetics and by extension their relevance as a proxy of groundwater residence time, fundamental parameter documenting the long term sustainability of the hydrosystem.

Timescales of regional circulation of saline fluids in continental crystalline rock aquifers (Armorican Massif, western France)

In recent decades, saline fluids have been sampled worldwide at great depths in continental basements. Although some of them have been attributed to marine transgressions , the mechanisms allowing their circulation are not understood. In this paper, we describe the horizontal and vertical distributions of moderately saline fluids (60 to 1400 mg L −1) sampled at depths ranging from 41 to 200 m in crystalline rock aquifers on the regional scale of the Ar-morican Massif (northwestern France). The horizontal and vertical distributions of high chloride concentrations are in good agreement with both the altitudinal and vertical limits and the succession of the three major transgressions between the Mio-Pliocene and Pleistocene ages. The mean chloride concentration for each transgression area is exponentially related to the time spanned until the present. It defines the potential laws of leaching (displacement) of marine waters by fresh meteoric waters. The results of the Armorican aquifers provide the first observed constraints for the timescales of seawater circulation in the continental crystalline basement and the subsequent leaching by fresh meteoric waters. The general trend of increasing chloride concentration with depth and the time frame for the flushing process provide useful information to develop conceptual models of the paleo-functioning of Armorican aquifers.

Impact of irrigated agriculture on groundwater resources in a temperate humid region

The groundwater irrigation expansion, and its multiple potential impacts on the quantity and quality of water resources, is not just restricted to areas that are water limited. In this study we present the seasonal impacts irrigation practices can have on groundwater resources in a temperate humid region, where the average annual rain/PET ratio is 1.0. In this system the irrigation expansion is solely supported by groundwater pumping, but despite this only 5 boreholes are monitored for hydraulic head data. In this study, we compensate the scarce hydrophysical dataset by incorporating environmental tracers (major ions, δ18O, δ2H and δ13C) and dating tracers (3H, CFC, SF6 and 14C). Results indicate that at 9 of the 15 irrigation sites investigated, groundwater pumping for irrigation has induced the mixing of recent groundwater (up to <1year) with older waters. The origin of the older waters was from either the deeper marl aquifer, or the shallow sand-clay aquifer (SCB) that has a 14C mean residence time (MRT) of up to 9700years. Secondly, although high nitrate loads in infiltrating waters were being diverted via the artificial subsurface drainage system, increases in fertiliser loads have resulted in higher NO3 concentrations in younger groundwater (NO3: 9-45mg/L, MRT <20years), compared with older groundwater (NO3≤9mg/L, MRT>20years). The changes in flow pathways, induced by irrigation, also results in seasonal declines in groundwater NO3 concentrations due to mixing with older waters. In temperate humid areas, such evaluations of the seasonal evolution of water residence time, mixing process, and agrochemical contaminants are an important contribution to real water resources management in irrigated catchments.

Autotrophic denitrification supported by biotite dissolution in crystalline aquifers: (2) transient mixing and denitrification dynamic during long-term pumping

We investigated the mixing and dynamic of denitrification processes induced by long-term pumping in the crystalline aquifer of Ploemeur (Brittany, France). Hydrological and geochemical parameters have been continuously recorded over 15 boreholes in 5km2 on a 25-year period. This extensive spatial and temporal monitoring of conservative as well as reactive compounds is a key opportunity to identify aquifer-scale transport and reactive processes in crystalline aquifers. Time series analysis of the conservative elements recorded at the pumped well were used to determine mixing fractions from different compartments of the aquifer on the basis of a Principal Component Analysis approach coupled with an end-member mixing analysis. We could reveal that pumping thus induces a thorough reorganization of fluxes known as capture, favoring infiltration and vertical fluxes in the recharge zone, and upwelling of deep and distant water at long-term time scales. These mixing fractions were then used to quantify the extent of denitrification linked to pumping. Based on the results from batch experiments described in a companion paper, our computations revealed that i) autotrophic denitrification processes are dominant in this context where carbon sources are limited, that ii) nitrate reduction does not only come from the oxidation of pyrite as classically described in previous studies analyzing denitrification processes in similar contexts, and that iii) biotite plays a critical role in sustaining the nitrate reduction process. Both nitrate reduction, sulfate production as well as fluor release ratios support the hypothesis that biotite plays a key role of electron donor in this context. The batch-to-site similarities support biotite availability and the role by bacterial communities as key controls of nitrate removal in such crystalline aquifers. However, the long term data monitoring also indicates that mixing and reactive processes evolve extremely slowly at the scale of the decade.

Autotrophic denitrification supported by biotite dissolution in crystalline aquifers (1): New insights from short-term batch experiments

We investigate denitrification mechanisms through batch experiments using crushed rock and groundwater from a granitic aquifer subject to long term pumping (Ploemeur, France). Except for sterilized experiments, extensive denitrification reaction induces NO3 decreases ranging from 0.3 to 0.6mmol/L. Carbon concentrations, either organic or inorganic, remain relatively stable and do not document potential heterotrophic denitrification. Batch experiments show a clear effect of mineral dissolution which is documented through cation (K, Na, Ca) and Fluoride production. These productions are tightly related to denitrification progress during the experiment. Conversely, limited amounts of SO4, systematically lower than autotrophic denitrification coupled to sulfur oxidation stoichiometry, are produced during the experiments which indicates that sulfur oxidation is not likely even when pyrite is added to the experiments. Analysis of cation ratios, both in isolated minerals of the granite and within water of the batch, allow the mineral dissolution during the experiments to be quantified. Using cation ratios, we show that batch experiments are characterized mainly by biotite dissolution. As biotite contains 21 to 30% of Fe and 0.3 to 1.7% of F, it constitutes a potential source for these two elements. Denitrification could be attributed to the oxidation of Fe(II) contained in biotite. We computed the amount of K and F produced through biotite dissolution when entirely attributing denitrification to biotite dissolution. Computed amounts show that this process may account for the observed K and F produced. We interpret these results as the development of microbial activity which induces mineral dissolution in order to uptake Fe(II) which is used for denitrification. Although pyrite is probably available, SO4 and cation measurements favor a large biotite dissolution reaction which could account for all the observed Fe production. Chemical composition of groundwater produced from the Ploemeur site indicates similar denitrification processes although original composition shows mainly plagioclase dissolution.

Delayed nitrate dispersion within a coastal aquifer provides constraints on land-use evolution and nitrate contamination in the past

Identifying sources of anthropogenic pollution, and assessing the fate and residence time of pollutants in aquifers is important for the management of groundwater resources, and the ecological health of groundwater dependent ecosystems. This study investigates anthropogenic contamination in the shallow alluvial aquifer of the Marana-Casinca, hydraulically connected to the Biguglia lagoon (Corsica, France). A multi-tracer approach, combining geochemical and environmental isotopic data (δ18O-H2O, δ2H-H2O, 3H, δ15N-NO3-, δ18O-NO3-, δ11B), and groundwater residence-time tracers (3H and CFCs) was carried out in 2016, and integrated with a study of land use evolution in the catchment during the last century. Groundwater NO3- concentrations, ranged between 2 mg/L and up to 30 mg/L, displaying the degradation of groundwater quality induced by anthropogenic activities (agricultural activities). Comparatively high δ15N-NO3- values (up to 19.7‰) in combination with δ11B values that were significantly lower (between 23‰ and 26‰) than the seawater background are indicative of sewage contamination. The ongoing deterioration of groundwater quality can be attributed to the uncontrolled urbanization development all over the alluvial plain, with numerous sewage leakages from the sanitation network and private sewage systems. Integration of contaminant and water-residence time data revealed a progressive accumulation of pollutants with time in the groundwater, particularly in areas with major anthropogenic pressure and slow dynamic groundwater flow. Our approach provides time-dependent insight into nitrogen pollution in the studied aquifer over the past decades, revealing a systematic change in the dominant NO3- source, from agricultural to sewage contamination. Yet, todays low groundwater quality is to large parts due to legacy pollution from land-use practices several decades ago, underlining the poor self-remediating capacity of this hydrosystem. Our results can be taken as warning that groundwater pollution that happened in the recent past, or today, may have dire impacts on the quality of groundwater-dependent ecosystems in the future.