Luc Aquilina

Origin, evolution and residence time of saline thermal fluids (Balaruc springs, southern France): implications for fluid transfer across the continental shelf

Thermal fluids in the Balaruc-les-Bains peninsula, on the northeastern edge of the Thau lagoon (southern France), supply the third largest spa in France. These thermal fluids interact with karst water in the Upper Jurassic aquifer composed of limestone and dolomite, forming two massifs to the east and north of the lagoon. These calcareous formations extend under the western end of the Thau lagoon. Geochemical and isotope analyses were carried out in 1996 and 1998 on the thermal wells of the Balaruc-les-Bains peninsula to determine the origin of the thermal fluids and their interaction with subsurface karst water. The thermal fluids are a mixture of karst water and water of marine origin.3H and NO3 concentrations show that the proportion of present-day karst water in certain thermal wells is small (<5%), thus enabling us to define a “pure” thermal end-member. The thermal end-member is itself a mixture of seawater and meteoric paleowater. Ca and Sr concentrations indicate a lengthy interaction with the carbonate substratum of the deep reservoir. Sr isotope signatures are very homogeneous and associated mainly with the dissolution of Jurassic carbonate, but also to evaporitic minerals. δ13C contents indicate that this dissolution is linked to deep inflow of CO2. 87Sr, trace element and rare earth element (REE) concentrations indicate that there is also a component, with a systematically minor participation, whose origin is deeper than the Jurassic carbonate and attributed to the Triassic and/or to the crystalline basement. 36Cl concentrations are extremely low, indicating a residence time of around a hundred thousand years. The outflow temperature of the thermal fluids reaches 50 °C, and geothermometers indicate a reservoir temperature of around 80–100 °C, locating this aquifer at a depth of between 2000 and 2500 m. The geometry of the geological formations indicates a thrust plane associated with major basement faulting that separates the two calcareous massifs and seems to control the rise of deep thermal fluids from the Jurassic carbonate reservoirs and the participation of a deeper component from the basement and/or the Triassic. The present study shows that seawater can infiltrate at great depths and reside for long periods of time compared to the subsurface groundwater cycle. Compared to other highly saline fluids encountered in basement zones, these waters have a relatively well-preserved marine signature, probably due to the carbonate nature of the aquifer in which the fluids resided and their short residence time.

Geochemistry and water dynamics of a medium-sized watershed: the Hérault, southern France: 1. Organisation of the different water reservoirs as constrained by Sr isotopes, major, and trace elements

Abstract The aim of this study of the Herault watershed is to constrain the river–groundwater relations with a global geochemical investigation: major and trace elements, radiogenic isotopes (Sr, Pb) and stable isotopes (oxygen, deuterium). Among the six sampling campaigns in high and low flows, this paper focuses on the first one (March 1995) sampled during a low flow period for major and trace elements and Sr isotopes on both dissolved and particulate loads. A companion paper will focus on the river–karst relations in a dynamical scheme over a complete hydrological cycle. The objective of this paper is to constrain the spatial organisation of the different water reservoirs, to show the relations between surficial and groundwaters and to assess the mechanical and chemical weathering in this low-flow period. The Herault main stream successively drains a Palaeozoic basement, a karstified Mesozoic cover and a Tertiary and Quaternary alluvial plain, the different tributaries also drain these lithologies. This watershed is also impacted by ancient mining, and agricultural activities especially in the southern part. Major element concentrations generally reflect the drained lithologies. The chemistry of the Herault main stream is mainly controlled by silicate and carbonate endmembers, whereas the karstic springs show clearly a mixture of limestones and dolomitic limestones. Major elements point out some specific characteristics of some karstic springs, and Sr isotopes are used to check previous underground circulation hypotheses and sometimes reveal strong connections with overlying surface waters. Mixing phenomena between the Herault river and its tributaries can be quantified in the 87 Sr / 86 Sr vs. 87 Rb / 86 Sr diagram based on a simple two-component scheme and agree within 10% with the real discharge measurements. As in large basins, the suspended matter presents more variable and more radiogenic 87 Sr / 86 Sr than the dissolved load, due to the more important contribution of silicate particles which are less soluble than carbonate. Dissolved Ca fluxes were estimated to be 36, 51 and 38 kg km −2 day −1 in the Palaeozoic basement, the Mesozoic cover and the alluvial plain, respectively. This implies a chemical erosion estimated to be 20 μm/year in the Palaeozoic basement and 58 μm/year in the Mesozoic cover, similar to values calculated for large basins.

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.

Origins and processes of groundwater salinization in the urban coastal aquifers of Recife (Pernambuco, Brazil): A multi-isotope approach

In the coastal multilayer aquifer system of a highly urbanized southern city (Recife, Brazil), where groundwaters are affected by salinization, a multi-isotope approach (Sr, B, O, H) was used to investigate the sources and processes of salinization. The high diversity of the geological bodies, built since the Atlantic opening during the Cretaceous, highly constrains the heterogeneity of the groundwater chemistry, e.g. Sr isotope ratios, and needs to be integrated to explain the salinization processes and groundwater pathways. A paleoseawater intrusion, most probably the 120 kyB.P. Pleistocene marine transgression, and cationic exchange are clearly evidenced in the most salinized parts of the Cabo and Beberibe aquifers. All (87)Sr/(86)Sr values are above the past and present-day seawater signatures, meaning that the Sr isotopic signature is altered due to additional Sr inputs from dilution with different freshwaters, and water-rock interactions. Only the Cabo aquifer presents a well-delimitated area of Na-HCO3 water typical of a freshening process. The two deep aquifers also display a broad range of B concentrations and B isotope ratios with values among the highest known to date (63-68.5‰). This suggests multiple sources and processes affecting B behavior, among which mixing with saline water, B sorption on clays and mixing with wastewater. The highly fractionated B isotopic values were explained by infiltration of relatively salty water with B interacting with clays, pointing out the major role played by (palaeo)-channels for the deep Beberibe aquifer recharge. Based on an increase of salinity at the end of the dry season, a present-day seawater intrusion is identified in the surficial Boa Viagem aquifer. Our conceptual model presents a comprehensive understanding of the major groundwater salinization pathways and processes, and should be of benefit for other southern Atlantic coastal aquifers to better address groundwater management issues.

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.

Nutrient dynamics in interstitial habitats of low-order rural streams with different bedrock geology

We Studied water exchange, nutrient dynamics, and microbial activities between the Surface and interstitial habitats of six low-order streams with catchments dominated by agriculture during high and low water periods. In each stream, surface (open) water and interstitial water form downwelling and Upwelling zones were considered. Interstitial habitats of most streams acted as a sink for nitrate, but as a source for ammonium and soluble reactive phosphorus (SRP). The nitrate sink persisted in shallow sediments of downwelling zones, while the source of ammonium and SRP persisted in deeper sediments of upwelling zones, where organic matter was decomposed and microbial uptake was lower than the production of nutrients. Geology (granite versus schist substratum) was the main variable controlling the nutrient contents and the microbial activity within interstitial habitats due to varying sediment grain size and hydraulic properties. Schist streams had the finest sediment grain size and lowest hydrologic connectivity between Surface water and interstitial habitats, and had the highest potential microbial activities, especially for denitrification. Land-use of the catchments (percentage of forested area), channel morphology (river incision), and local characteristics of the benthic sediment (partial clogging) also influenced nutrient concentrations and microbial activities irrespectively of the geology of the catchment.

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.

Long-Term Effects of High Nitrogen Loads on Cation and Carbon Riverine Export in Agricultural Catchments

The intensification of agriculture in recent decades has resulted in extremely high nitrogen inputs to ecosystems. One effect has been H(+) release through NH(4)(+) oxidation in soils, which increases rock weathering and leads to acidification processes such as base-cation leaching from the soil exchange complex. This study investigated the evolution of cation concentrations over the past 50 years in rivers from the Armorican crystalline shield (Brittany, western France). On a regional scale, acidification has resulted in increased base-cation riverine exports (Ca(2+), Mg(2+), Na(+), K(+)) correlated with the increased NO(3)(-) concentration. The estimated cation increase is 0.7 mmol(+)/L for Ca(2+) + Mg(2+) and 0.85 mmol(+)/L for total cations. According to mass balance, cation loss represents >30% of the base-cation exchange capacity of soils. Long-term acidification thus contributes to a decline in soil productivity. Estimates of the total organic nitrogen annually produced worldwide indicate that acidification may also constitute an additional carbon source in crystalline catchments if compensated by liming practices.

Reaction chain modeling of denitrification reactions during a push–pull test

Field quantitative estimation of reaction kinetics is required to enhance our understanding of biogeochemical reactions in aquifers. We extended the analytical solution developed by Haggerty et al. (1998) to model an entire 1st order reaction chain and estimate the kinetic parameters for each reaction step of the denitrification process. We then assessed the ability of this reaction chain to model biogeochemical reactions by comparing it with experimental results from a push-pull test in a fractured crystalline aquifer (Ploemeur, French Brittany). Nitrates were used as the reactive tracer, since denitrification involves the sequential reduction of nitrates to nitrogen gas through a chain reaction (NO3(-)→NO2(-)→NO→N2O→N2) under anaerobic conditions. The kinetics of nitrate consumption and by-product formation (NO2(-), N2O) during autotrophic denitrification were quantified by using a reactive tracer (NO3(-)) and a non-reactive tracer (Br(-)). The formation of reaction by-products (NO2(-), N2O, N2) has not been previously considered using a reaction chain approach. Comparison of Br(-) and NO3(-) breakthrough curves showed that 10% of the injected NO3(-) molar mass was transformed during the 12 h experiment (2% into NO2(-), 1% into N2O and the rest into N2 and NO). Similar results, but with slower kinetics, were obtained from laboratory experiments in reactors. The good agreement between the model and the field data shows that the complete denitrification process can be efficiently modeled as a sequence of first order reactions. The 1st order kinetics coefficients obtained through modeling were as follows: k1=0.023 h(-1), k2=0.59 h(-1), k3=16 h(-1), and k4=5.5 h(-1). A next step will be to assess the variability of field reactivity using the methodology developed for modeling push-pull tracer tests.

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.