Thierry Labasque

Spatial variability of phytoplankton composition and biomass on the eastern continental shelf of the Bay of Biscay (north-east Atlantic Ocean). Evidence for a bloom of Emiliania huxleyi (Prymnesiophyceae) in spring 1998

A coccolithophorid bloom, dominated by Emiliania huxleyi, was detected by sea viewing wide field of view sensor (SeaWiFS) images on the French continental shelf break in April 1998. Concentrations of up to 3.2 � 10 6 coccospheres l � 1 and up to 8.6 � 10 7 coccoliths l � 1 were measured by microscope countings of samples taken during the first days of the bloom. Moderate chlorophyll a concentrations (range: 0.8–1.1m gl � 1 ) characterised the study area. Chlorophyll and carotenoid pigments, analysed by high performance liquid chromatography (HPLC), confirmed the dominance of Pry-mnesiophytes in the bloom area. The bloom was not monospecific and diatoms, mainly belonging to the genus Rhizosolenia, as well as silicoflagellates were observed in the phytoplankton. Outside of the bloom area, ‘‘green algae’’ and cryptophytes dominated the phytoplankton. Diatoms were a dominant group of the Vilaine plume community and dinoflagellates were dominant in the southern part of the study area. The development of the dissipative phase of coccolithophorid bloom and its persistence for at least 4 weeks is explained by the conjunction of water mass preconditioning by river inputs on the continental shelf, increasing PAR during spring, and internal wave formation at the shelf break during spring tides. Partial dissolving of coccoliths and lack of horizontal displacement of the bloom, during the 4 weeks, are interpreted in terms of rapid settling of coccoliths due to packaging by grazers as well as ongoing pro-duction maintained by nutrient injection via the action of internal waves. r 2002 Elsevier Science Ltd. All rights reserved.

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.

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.

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.

Glacial recharge, salinisation and anthropogenic contamination in the coastal aquifers of Recife (Brazil)

Implying large residence times and complex water origins deep coastal aquifers are of particular interest as they are remarkable markers of climate, water use and land use changes. Over the last decades, the Metropolitan Region of Recife (Brazil) went through extensive environmental changes increasing the pressure on water resources and giving rise to numerous environmental consequences on the coastal groundwater systems. We analysed the groundwater of the deep aquifers Cabo and Beberibe that are increasingly exploited. The processes potentially affecting groundwater residence times and flow paths have been studied using a multi-tracer approach (CFCs, SF6, noble gases, 14C, 2H and 18O). The main findings of these investigations show that: (1) Groundwaters of the Cabo and Beberibe aquifers have long residence times and were recharged about 20,000years ago. (2) Within these old groundwaters we can find palaeo-climate evidences from the last glacial period at the tropics with lower temperatures and dryer conditions than the present climate. (3) Recently, the natural slow dynamic of these groundwater systems was significantly affected by mixing processes with contaminated modern groundwater coming from the shallow unconfined Boa Viagem aquifer. (4) The large exploitation of these aquifers leads to a modification of the flow directions and causes the intrusion through palaeo-channels of saline water probably coming from the Capibaribe River and from the last transgression episodes. These observations indicate that the current exploitation of the Cabo and Beberibe aquifers is unsustainable regarding the long renewal times of these groundwater systems as well as their ongoing contamination and salinisation. The groundwater cycle being much slower than the human development rhythm, it is essential to integrate the magnitude and rapidity of anthropogenic impacts on this extremely slow cycle to the water management concepts.

Groundwater contamination in coastal urban areas: Anthropogenic pressure and natural attenuation processes. Example of Recife (PE State, NE Brazil)

In a context of increasing land use pressure (over-exploitation, surface-water contamination) and repeated droughts, identifying the processes affecting groundwater quality in coastal megacities of the tropical and arid countries will condition their long-term social and environmental sustainability. The present study focuses on the Brazilian Recife Metropolitan Region (RMR), which is a highly urbanized area (3,743,854 inhabitants in 2010) on the Atlantic coast located next to an estuarial zone and overlying a multi-layered sedimentary system featured by a variable sediment texture and organic content. It investigates the contamination and redox status patterns conditioning potential attenuation within the shallow aquifers that constitute the interface between the city and the strategic deeper semi-confined aquifers. These latter are increasingly exploited, leading to high drawdown in potenciometric levels of 20-30m and up to 70m in some high well density places, and potentially connected to the surface through leakage. From a multi-tracer approach (major ions, major gases, δ(11)B, δ(18)O-SO4, δ(34)S-SO4) carried out during two field campaigns in September 2012 and March 2013 (sampling of 19 wells and 3 surface waters), it has been possible to assess the contamination sources and the redox processes. The increasing trend for mineralization from inland to coastal and estuarial wells (from 119 to around 10,000μS/cm) is at first attributed to water-rock interactions combined with natural and human-induced potentiometric gradients. Secondly, along with this trend, one finds an environmental pressure gradient related to sewage and/or surface-channel network impacts (typically depleted δ(11)B within the range of 10-15‰) that are purveyors of chloride, nitrate, ammonium and sulfate. Nitrate, ammonium and sulfate (ranging from 0 to 1.70mmol/L, from 0 to 0,65mmol/L, from 0.03 to 3.91mmol/L respectively are also potentially produced or consumed through various redox processes (pyrite oxidation, denitrification, dissimilatory nitrate reduction to ammonium) within the system, as is apparent within a patchwork of biogeochemical reactors. Furthermore, intensive pumping in the coastal area with its high well density punctually leads to temporary well salinization ([Cl] reaching temporarily 79mmol/L). Our results, summarized as a conceptual scheme based on environmental conditions, is a suitable basis for implementing sustainable management in coastal sedimentary hydrosystems influenced by highly urbanized conditions.

Geochemical tracing and modeling of surface and deep water–rock interactions in elementary granitic watersheds (Strengbach and Ringelbach CZOs, France)

From the study of the Strengbach and Ringelbach watersheds we propose to illustrate the interest of combining the geochemical tracing and geochemical modeling approaches on surface and deep borehole waters, to decipher the diversity of the water flow and the associated water–rock interactions in such elementary mountainous catchments. The results point to a clear geochemical typology of waters depending on the water circulations (deep vs. hypodermic) within the substratum.