Emerging organic compounds as markers of the degradation of groundwater qualitative and quantitative equilibrium in a context of rapid urban expansion.

With the neo-metamorphosis of the residential landscape worldwide and sluggish sanitation strategies in urban environments, rudimentary on-site sanitation systems remain commonly used, especially in developing countries, despite the risks of groundwater contamination. The effective management of such water resources relies on assessment of the sensitivity of anthropized aquifers to man-made impact, including groundwater behavioural alteration, in terms of both quality and quantity. Associated with tracking of changes in land use, this study proposes an approach involving emerging organic contaminants (EOCs) as indicators of the alteration of groundwater balance due the exposure of shallow aquifers to the risks of infiltration of untreated wastewater from soak pits. This methodology was applied to the shallow aquifer beneath the urban agglomeration of Grand-Sfax (Tunisia). Combined with an updated follow-up of groundwater piezometric fluctuations in relation with inputs from surface contamination sources, the spatialisation of contamination levels by EOCs provided a clear delineation of the most impacted aquifer zones. This approach revealed a significant link between the continuous rise in piezometric levels by contributions from untreated inputs and the accumulation of high levels of contamination in groundwater. The understanding of EOC underground pathways allowed the determination of the fates and processes responsible for the diffusion of contamination throughout the studied aquifer. The ability of groundwater to reflect population life style and the use patterns of such organic molecules was also assessed. Besides revealing the legacy of persistent contamination, this approach involving EOCs as tracers with different levels of persistence provided a spatial observation of the aquifer exposure to continuous contamination processes. This approach made it possible to develop a conceptual presentation of aquifer vulnerability to urban pressures and to predict the effects of subsequent expansion of unplanned urbanisation on groundwater quality.

Socio-hydrogeological survey and assessment of organic pollutants to highlight and trace back pollution fluxes threatening a coastal groundwater-dependent ecosystem.

Despite being a vector of pollution towards connected ecosystems, groundwater is often underestimated or not taken into account in management frameworks. To fill this gap, we propose to add socio-economic data to hydrogeological investigations to identify past and present pollution sources linked to human activities at watershed scale in order to forecast threats towards groundwater-dependent ecosystems (GDEs). The aim of this paper is to demonstrate, by a cross-disciplinary approach, the added value of socio-hydrogeological investigations to tackle anthropogenic pollution fluxes towards a GDE and to contribute to more sustainable management of groundwater resources. A survey combining chemical compounds analysis, data compilation, land use analysis and field investigations with a questionnaire was carried out on the Biguglia lagoon plain (France). Results show a pollution with a two-fold source, both agricultural and domestic, in all water bodies of the plain. The pesticide analysis reveals the presence of 10 molecules, including domestic compounds, with concentrations exceeding European groundwater quality standards for individual pesticides, as well as pesticides already banned for twenty years. On the basis of both the field survey and the questionnaire, agricultural pollution has been identified as very local highlighting the storage capacity of the aquifer, whereas domestic pollution is diffuse over the plain and attributed to sewage network effluents and septic tanks. Domestic compounds present shorter residence time within the aquifer highlighting continuous inputs, related to consumption habits of the population. Under the Water Framework Directive (WFD), member states are required to preserve the good ecological status, quality and quantity of water bodies. However, for GDEs it is difficult to achieve the 'good status' required without considering the groundwater's pollutant storage capacity and pollution legacy. To help resolve this issue, socio-hydrogeology has proved to be an efficient tool as well as for implementing effective protection measures for Mediterranean GDEs.

The role of groundwater in CO2 production and carbon storage in Mediterranean peatlands: An isotope geochemistry approach.

Peatlands are permanent wetlands recognized for ecosystem services such as biodiversity conservation and carbon storage capacity. Little information is available about their response to global change, the reason why most Earth system climate models consider a linear increase in the release of greenhouse gases (GHG), such as CO2, with increasing temperatures. Nevertheless, numerous studies suggest that an increase in the temperature may not imply a decrease in photosynthesis and carbon storage rates if water availability is sufficient, the latter being under the control of local hydrology mechanisms. Mediterranean peatlands well illustrate this fact. Since they are groundwater-dependent, they are hydrologically resilient to the strong seasonality of hydroclimatic conditions, especially during the summer drought. In the present study, we demonstrate that, even if such peatlands release CO2 into the atmosphere, they can maintain a carbon storage capacity. To this end, a geochemical study disentangles the origin and fate of carbon within a Mediterranean peatland at the watershed scale. Field parameters, major ions, dissolved organic and inorganic carbon content and associated δ13C values allow for characterizing the seasonality of hydrochemical mechanisms and carbon input from an alluvial aquifer (where rain, river, shallow, and deep groundwater flows are mixing) to the peatland. The inorganic and organic content of peat soil and δ13C values of total organic matter and CO2 complete the dataset, making it possible to provide arguments in favour of lower organic matter oxidation compared to primary production. Overall, this study highlights the groundwater role in the fluxes of CO2 at the peatland-atmosphere interface, and more broadly the need to understand the interactions between the water and carbon cycles to build better models of the future evolution of the global climate.

Shallow Quaternary groundwater in the Lake Chad basin is resilient to climate change but requires sustainable management strategy: Results of isotopic investigation.

Within the Lake Chad Basin, the unconfined Quaternary aquifer offers permanent and easy access to water resources. This transboundary regional aquifer is shared by Chad, Niger, Nigeria and Cameroon and extends over ~500,000 km2. Climatic conditions and repeated droughts as well as the intensification of agriculture in the region have multiple negative impacts on the aquifer such as changes in groundwater level and its quality. Being a strategic water resource for the whole Chadian region, the groundwater potential of the Quaternary aquifer must be better characterized and understood to evaluate its resilience to climate change and anthropogenic impact. Stable isotopes and tritium of the water molecule were used to estimate water origin and residence time at the regional scale and to elucidate the interconnections between the different hydrological and hydrogeological components. Results show active recharge processes to the Quaternary aquifer as well as dynamic connections with surface waters (both river courses and wetlands) but also indicate less dynamic behavior of the Quaternary groundwater resource in some areas of the region. Based on the isotopic investigations, the Quaternary aquifer in the Chad basin was found to be resilient to climate change but its hydrogeological specificities (dependence to surface water from the upstream basins and transboundary nature of its structure) can make it prone to inadequate management strategies.

The challenge of assessing the proper functioning conditions of coastal lagoons to improve their future management.

The sustainable management of coastal lagoon hydrosystems is a key issue for the socio-economic and environmental development of many coastal areas worldwide. Often maintained by direct or indirect groundwater supplies, they provide a large range of ecosystem services, from which human societies take advantage. Twenty years after its implementation, a large majority of the Mediterranean lagoons have still not reached the "good status" required by the WFD. Several questions then arise as to the representativeness of the WFD indicators or the relevance of the restoration objectives considering the complexity, evolutionary and unpredictable nature of lagoon hydrosystems. This study proposes an innovative, multidisciplinary, long-term approach to define the proper functioning conditions of a costal lagoon hydrosystems, i.e. all the factors that contribute to the functioning of coastal lagoon hydrosystems and the connectivity with other biodiversity reservoirs, be they ecological, hydrological, social or political. By considering the lagoons and all its hydrological, ecological and societal proper functioning conditions over almost 200 years, this approach makes it possible to assess the influence of past natural and anthropogenic disturbances and support the implementation of future relevant hydrosystem-based management plans which have to be coordinated and politically driven. Defining proper restoration and management objectives should ensure that ecological functions are maintained based on current and future ecosystem benefits and uses. Considering the highly unpredictable nature of coastal hydrosystems, the state of an ecosystem should not only be evaluated on ecological or chemical criteria but also take into account socio-economic and political indicators. The implementation of the 3rd river basin management plan of the WFD as soon as 2022 could be the appropriate occasion to reassess the restoration objectives towards more realistic goals and to give more significance to the definition of the "resilience capacity" of water bodies in place of inappropriate restricted restauration objectives.

Assessing the hydrogeological resilience of a groundwater-dependent Mediterranean peatland: Impact of global change and role of water management strategies.

Mediterranean peatlands remain largely under-documented, except for detailed biological data such as fauna and flora taxa lists, and yet are increasingly threatened by water withdrawal and agriculture practices. This lack of information, particularly on their hydrogeological functioning, makes it impossible to evaluate their response to changing climate conditions. A pilot study on a representative Mediterranean peatland on the island of Corsica (France) was conducted to evaluate recharge modalities in the peatland using a coupled water-level monitoring, geochemical and isotope multi-tracing approach (electric conductivity, major ions, δ18O, δ2H, 3H, 87Sr/86Sr). The goal was to understand how water budgets in peatland ecosystems were maintained throughout the year, especially during the summer. Despite the remarkable stability of the peatland water level, the recharge contributions of varied water bodies through an alluvial aquifer vary significantly from one season to another. An end-member mixing analysis (EMMA) indicates that the peatland is mainly recharged by an alluvial aquifer. During fall-winter, the alluvial aquifer on which the peatland depends is recharged by the rainfall, a river, and shallow groundwater (colluvium). During spring-summer, water supply is provided mostly by a river, shallow, and deep groundwater (fractured granite). However, this specific hydrogeological functioning is not taken into account by environmental management policies making peatlands vulnerable to anthropogenic and climatic pressures. Thus, their actual status regarding water and aquatic environment management policies is discussed to provide recommendations for better consideration and preservation.

Shallow urban aquifers under hyper-recharge equatorial conditions and strong anthropogenic constrains. Implications in terms of groundwater resources potential and integrated water resources management strategies.

Humid equatorial regions are recognized as the least documented in term of hydrogeological functioning of aquifers despite the fact that they house a lot of developing countries and that groundwater is often the main water resource. Regarding this aspect, a study was conducted in sub-Saharan Africa, focusing on the Mio-Pliocene aquifer in Douala megacity (Cameroon) which is the rainiest city in West-Africa (about 4000 mm/year) with one of the greatest demographic growth rate of the African continent. Firstly, groundwater recharge rate has been calculated through water balance and Water Table Fluctuation methods. Results show that the aquifer is characterized by a high recharge of 600-760 mm/year. Then infiltration process and groundwater flow conditions have been examined by combining hydrogeological and isotopic methods. Rainwater infiltrated is recycled in the vadose zone through plants roots transpiration and groundwater flows with a Darcy velocity of 5 m/day. From the recharge area to the estuary, the mineralization increases controlled by anthropogenic activities and water-rocks interactions which are amplified by the residence time and accelerated by the hot and humid climate of Douala. The paper ends with the determination of natural background levels (NBLs) and threshold values (TV) of chemical components in groundwater to assess the contamination for different flow paths. This multi-proxy study and the establishment of NBLs and TV can be beneficial to improve groundwater resources management. Moreover, the conceptual model provided in this study could be used as a reference for porous aquifers submitted to high rainfall amount.

Temporal offset between precipitation and water uptake of Mediterranean pine trees varies with elevation and season.

For climate models that use paleo-environment data to predict future climate change, tree-ring isotope variations are one important archive for the reconstruction of paleo-hydrological conditions. Due to the rather complicated pathway of water, starting from precipitation until its uptake by trees and the final incorporation of its components into tree-ring cellulose, a closer inspection of seasonal variations of tree water uptake is important. In this study, branch and needle samples of two pine species (Pinus pinaster and Pinus nigra subsp. laricio) and several water compartments (precipitation, creek, soil) were sampled over a two-year period and analyzed for the temporal variations of their oxygen and hydrogen stable isotope ratios (δ18O and δ2H) at five sites over an elevation gradient from sea level to around 1600 m a.s.l. on the Mediterranean island of Corsica (France). A new model was established to disentangle temporal relationships of source water uptake of trees. It uses a calculation method that incorporates the two processes mostly expected to affect source water composition: mixing of waters and evaporation. The model results showed that the temporal offset from precipitation to water uptake is not constant and varies with elevation and season. Overall, seasonal source water origin was shown to be dominated by precipitation from autumn and spring. While autumn precipitation was a more important water source for trees growing at mid- (~800-1000 m a.s.l) and high-elevation (~1600 m a.s.l.) sites, trees at coastal sites mostly took up water from late winter and spring. These findings show that predicted decreases in precipitation amounts during the wet season in the Mediterranean can have strong impacts on water availability for pine trees, especially at higher elevations.

Groundwater dependent ecosystems in coastal Mediterranean regions: Characterization, challenges and management for their protection.

Coastal lagoons deliver a wide range of valuable ecosystem goods and services. These ecosystems, that are often maintained by direct or indirect groundwater supplies, are collectively known as groundwater dependent ecosystems (GDEs). The importance of groundwater supplies is greatly exacerbated in coastal Mediterranean regions where the lack of surface water and the over-development of anthropogenic activities critically threaten the sustainability of coastal GDEs and associated ecosystem services. Yet, coastal GDEs do not benefit from a legal or managerial recognition to take into account their specificity. Particular attention should be paid to the characterization of environmental and ecological water requirements. The hydrogeological knowledge about the management and behavior of coastal aquifers and GDEs must be strengthened. These investigations must be supplemented by a stronger assessment of potential contaminations to develop local land-uses and human activities according to the groundwater vulnerability. The quantitative management of water resources must also be better supervised and/or more constrained in order to ensure the water needs necessary to maintain coastal GDEs. The transdisciplinary approach between hydrogeology, hydrology, social sciences and law is essential to fully understand the socio-economic and environmental complexity of coastal GDEs. Priority must now be given to the development of an appropriate definition of coastal GDEs, based on a consensus between scientists and lawyers. It is a necessary first step to develop and implement specific protective legislation and to define an appropriate management scale. The investment and collaboration of local water users, stakeholders and decision-makers need to be strengthened through actions to favor exchanges and discussions. All water resources in the coastal areas should be managed collectively and strategically, in order to maximize use efficiency, reduce water use conflicts and avoid over-exploitation. It is important to continue to raise public awareness of coastal aquifers at the regional level and to integrate their specificities into coastal zone management strategies and plans. In the global context of unprecedented anthropogenic pressures, hydro-food crises and climate change, environmental protection and preservation of coastal GDEs represents a major challenge for the sustainable socio-economic and environmental development of Mediterranean coastal zones.

Riverine carbon dioxide evasion along a high-relief watercourse derived from seasonal dynamics of the water-atmosphere gas exchange.

The high-relief catchment of the Tavignanu River (Corsica Island, France) with an elevation range from sea level to 2622 m above sea level was investigated for its riverine carbon budget and stable carbon isotopes. Major riverine dissolved inorganic carbon (DIC or TCO2) sources depended on seasons and sub-catchment lithology. In winter δ13CDIC values of -2 to -7‰ (VPDB) indicated influences of atmospheric CO2. δ13CDIC values decreased gradually to values between -9 and -12‰ in July, which indicates elevated soil CO2 contribution. An observed downstream increase in the total amount of carbon species correlated with inputs from carbonate bearing tributaries and evaporation effects in summer. Main channel partial pressure of CO2 (pCO2) was seasonally highly variable in the upper silicate catchment and the lower coastal plain, where summer values exceed up to six times atmospheric levels. During winter, the central section of the Tavignanu River was found to be undersaturated with respect to atmospheric CO2 levels. The median values for main channel pCO2 were below atmospheric levels in winter and spring and above in summer and autumn. The annual carbon flux across the air-water boundary (FCO2) along the Tavignanu River was calculated with (0.77 ±â€¯0.24) Gg C yr-1, which is about seven times higher than the riverine TCO2 transport to the sea of about 0.11 Gg C yr-1. While large sections of the river experienced year-round atmospheric CO2 uptake or equilibrium, the river as a whole was a small but continuous net source of carbon to the atmosphere. This underlines the important, but so far not well-constrained, contributions of smaller streams and rivers to the terrestrial carbon flux and the need of incorporating them into future global carbon cycle models.

Combinations of geoenvironmental data underline coastal aquifer anthropogenic nitrate legacy through groundwater vulnerability mapping methods.

Groundwater quality is strongly dependent on land use. Past and current anthropogenic activities can lead to the diffusion of contaminants in aquifers. This diffusion can threaten the resource exploitation for decades, thereby endangering the ecological health of groundwater dependent ecosystems. Thus, groundwater stakeholders need methods for long-term management which integrate groundwater vulnerability. This study was conducted on the shallow alluvial aquifer of the groundwater-dependent Biguglia lagoon on Corsica Island, France. The aquifer is exposed to anthropogenic contamination for many decades with nitrate contamination legacy linked to agricultural activities, uncontrolled urbanization and sewage leakages. In most cases, vulnerability mapping is done in the objective of comparing groundwater situation regarding an on-going contamination process. But the question is still pending for aquifers where contamination is inherited from past practices or contaminations and where anthropogenic influences have changed through time. To propose an effective and innovative method for territorial management in Mediterranean alluvial aquifers, four index-based groundwater vulnerability mapping methods were tested and compared: two intrinsic vulnerability mapping methods (DRASTIC and SINTACS) and two specific vulnerability mapping methods (Modified-DRASTIC and SI), the latter integrating land use in the accuracy of groundwater vulnerability. Novelty is coming from the comparison between vulnerability maps and their application and validation in a hydrosystem affected by nitrate legacy-type contamination. The specific vulnerability mapping methods are more likely to represent the current pressures to which groundwater are subject. Thus, specific vulnerability methods such as the SI one revealed here very relevant to assess groundwater quality and to react retrospectively. The comparison between groundwater nitrate legacy and intrinsic groundwater vulnerability methods appeared also useful to define priority protection areas in long-term territorial management planning (EU Water Framework Direction). In this sense, the SINTACS method seems to be the more appropriate in the Mediterranean and alluvial context of this study.

Priority substances and emerging pollutants in urban rivers in Ukraine: Occurrence, fluxes and loading to transboundary European Union watersheds.

The occurrence and fluxes of 18 priority substances and emerging pollutants listed in the European Union Water Framework Directive and a Watch List (trace metals (Cd, Pb and Ni), nonylphenols, octylphenols, 8 polyaromatic hydrocarbons, 4 dioxin-like polychlorinated biphenyls and diclofenac) were investigated in a Ukrainian city and the mass discharge loads of these compounds into EU-transboundary watersheds were estimated. Fluxes of chemicals were calculated per capita and per area of the Ukrainian urban territory and used to estimate mass loading of priority and emerging concern compounds from Lviv, Uzhorod and Chernivtsi (West Ukraine) to neighbouring EU-transboundary rivers. The highest loading was found for trace metals (1.15 t a-1), diclofenac (0.7 t a-1) and nonylphenols (0.4 t a-1). Transboundary water contamination must be considered in order to successfully manage water resources in a manner that fulfils the requirements of EU environmental quality standards.

An Analytical Method for Assessing Recharge Using Groundwater Travel Time in Dupuit-Forchheimer Aquifers.

An analytical solution to calculate the recharge of unconfined aquifers with Dupuit-Forchheimer type flow conditions is proposed. This solution is derived from an existing closed-form analytical solution initially developed to determine groundwater travel time when the recharge of the aquifer is known. This existing solution has been modified to determine recharge when groundwater travel time is known. An illustration is given with a field case example for the Bonifacio aquifer of the island of Corsica (France), in the Mediterranean. In this aquifer, previously established differences in groundwater residence time between two water samples were determined from anthropogenic atmospheric gas (chlorofluorocarbons and sulfur hexafluoride) measurements. The time difference is entered into the new analytical solution to determine recharge. The calculations yield a value of average recharge that agrees with the results obtained by several other methods that were presented in previous studies to assess the recharge of the Bonifacio aquifer. Also presented in this study is a sensitivity analysis of the new analytical solution, to quantify the influence of different parameters that control recharge: hydraulic conductivity, effective porosity and the groundwater travel time. This study illustrates how geochemical data can be combined with physical models to measure recharge. Such an approach could be adopted in other homogeneous aquifers worldwide that satisfy Dupuit-Forchheimer type flow conditions.

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.

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, today's 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.

Determination of dominant sources of nitrate contamination in transboundary (Russian Federation/Ukraine) catchment with heterogeneous land use.

Nitrate contamination of surface water and shallow groundwater was studied in transboundary (Russia/Ukraine) catchment with heterogeneous land use. Dominant sources of nitrate contamination were determined by applying a dual δ 15N-NO3 and δ 18O-NO3 isotope approach, multivariate statistics, and land use analysis. Nitrate concentration was highly variable from 0.25 to 22 mg L-1 in surface water and from 0.5 to 100 mg L-1 in groundwater. The applied method indicated that sewage to surface water and sewage and manure to groundwater were dominant sources of nitrate contamination. Nitrate/chloride molar ratio was added to support the dual isotope signature and indicated the contribution of fertilizers to the nitrate content in groundwater. Groundwater temperature was found to be an additional indicator of manure and sewerage leaks in the shallow aquifer which has limited protection and is vulnerable to groundwater pollution.

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.

Labile trace metal contribution of the runoff collector to a semi-urban river.

In this study, the distribution of labile trace metals (LTMs; Cd, Co, Cr, Cu, Ni, Pb, and Zn) in a semi-urban runoff collector was examined to assess its influence to a natural aqueous system (Jalle River, Bordeaux, France). This river is of high importance as it is part of a natural reserve dedicated to conserving aquatic flora and fauna. Two sampling campaigns with a differing precipitation condition (period 1, spring season; and period 2, summer season associated with storms) were considered. Precipitation and water flow were monitored. The collector is active as it is receptive to precipitation changes. It influences the river through discharging water, contributing LTMs, and channeling the mass fluxes. During period 2 where precipitation rate is higher, 25 % of the total water volume of the river was supplied by the collector. LTMs were detected at the collector. Measurements were done by using diffusive gradient in thin films (DGT) probes deployed during 1, 7, and 14 days in each period. The results showed that in an instantaneous period (day 1 or D1), most of these trace metals are above the environmental quality standards (Cd, Co, Cr, and Zn). The coefficient of determination (r (2) > 0.50) employed confirmed that the LTM concentrations in the downstream can be explained by the collector. While Co and Cr are from the upstream and the collector, Cd, Cu, and Zn are mostly provided by the collector. Ni, however, is mostly delivered by the upstream. Using the concentrations observed, the river can be affected by the collector in varying ways: (1) adding effect, resulting from the mix of the upstream and the collector (if upstream ˂ downstream); (2) diluted (if upstream ˃ downstream); and (3) conservative or unaffected (upstream ~ downstream). The range of LTM mass fluxes that the collector holds are as follows: (1) limited range or ˂10 g/day, Cd (0.04-1.75 g/day), Co (0.08-05.42 g/day), Ni (0.06-1.45 g/day), and Pb (0.08-9.89 g/day); (2) moderate range or 11-50 g/day, Cr (0.23-33.26 g/day) and Cu (0.77-37.88 g/day); and (3) wide range or ˃50 g/day, Zn (26.33-676.61 g/day). Hence, the collector is a major source of concern in terms of contamination. This is as the water with considerable LTMs is channeled openly to the river without any treatment.

Trends of labile trace metals in tropical urban water under highly contrasted weather conditions.

The spatio-temporal trend of trace metals (Cd, Co, Cr, Cu, Ni, Pb, and Zn) in a tropical urban estuary under the influence of monsoon was determined using diffusive gradient in thin films (DGT) in situ samplers. Three different climatic periods were observed: period 1, dry with dredging activity; period 2, intermediate meaning from dry to wet event; and period 3, wet having continuous rainfall. Conforming to monsoon regimes, these periods correspond to the following: transition from winter to summer, winter, and summer monsoons, respectively. The distinction of each period is defined by their specific hydrological and physico-chemical conditions. Substantial concentrations of the trace metals were detected. The distribution and trend of the trace metals under the challenge of a tropical climate were able to follow using DGT as a sensitive in situ sampler. In order to identify the differences among periods, statistical analyses were performed. This allowed discriminating period 2 (oxic water) as significantly different compared to other periods. The spatio-temporal analysis was then applied in order to distinguish the trend of the trace metals. Results showed that the trend of trace metals can be described according to their response to (i) seasonal variations (Cd and Cr), (ii) spatio-temporal conditions (Co, Cu, Ni, and Pb), and (iii) neither (i) nor (ii) meaning exhibiting no response or having constant change (Zn). The correlation of the trace metals and the physico-chemical parameters reveals that Cd, Co, Cu, and Cr are proportional to the dissolved oxygen (DO), Cd and Ni are correlated pH, and Zn lightly influenced by salinity.

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters.

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography-tandem MS electrospray ionization+/- (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: "stable" (Cd and Cr) and "time varying" (Cu, Zn, Ni, and Pb). The relationship Cd >> Cu > Ag > Cr ≥ Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb-Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.