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.

Nitrate sources and mixing in the Danube watershed: implications for transboundary river basin monitoring and management.

Dispersed and unknown pollution sources complicate water management in large transboundary watersheds. We applied stable isotopes of water and nitrate together with contaminants of emerging concern (CECs: carbamazepine, caffeine, sulfamethoxazole, perfluorooctanoic acid and 2,4-dinitrophenol) to evaluate mixing and inputs of water and contaminants from tributaries into the mainstem of the transboundary Danube River. Stable isotope (δ18O, δ2H) variations from low values (- 13.3 ‰, - 95.1 ‰) in the Upper Danube after the Inn River confluence to high values (- 9.9 ‰, - 69.7 ‰) at the Danube River mouth revealed snowmelt dominated tributary mixing (~ 70%) in the mainstem. Stable isotopes of nitrate (δ15N-NO3) in the Danube River varied from lower values (+ 6.7 ‰) in the Upper Danube to higher values after the mixing with Morava River (+ 10.5 ‰) and showed that cold snowmelt can reduce biological activity and controls nitrate biotransformation processes in the mainstem up to 1000 km downstream. Data on emerging contaminants affirmed the low biodegradation potential of organic compounds transferred into the mainstem by tributaries. We found pollutant source tracing in large rivers is complicated by mixing of multiple sources with overlapping isotopic signatures, but additional tracers such as CECs improve the interpretation of hydrological processes (e.g., water transit time) and support tracing of nitrate pollution sources, and biogeochemical processes. Our approach can be applied to other watersheds to improve the understanding of dilution and mixing processes. Moreover, it provides directions for improving national and transboundary water quality monitoring networks.

Temperature and precipitation effects on the isotopic composition of global precipitation reveal long-term climate dynamics.

Earth's climate history is traced through the long-term covariance between the isotopic (δ 18O) composition of archived meteoric waters (groundwater, ice cores) with air temperature (T) and amount of precipitation (P). To assess recent multi-decadal climatic changes, we analysed δ18O, T and P, and the relationships between these parameters at 20 stations having 60 years of continuous monthly isotopic records. Using nonparametric regressions and time series modelling we found significant linear and non-linear relationships for δ18O with T and P and showed that the δ18O dependency on these two parameters varied over decadal scales, thereby revealing complex relationships related to recycled moisture, large-scale convective processes and atmospheric-oceanic oscillations. Due to multiple factors controlling the δ 18O composition of precipitation including P and T effects, we found that time-varying relationships between δ18O in precipitation P and T were better explained using the non-linear regressions. Our results affirmed that δ18O distributions in global precipitation are integrative indicators of climate dynamics whose patterns can be applied to better understand region-specific climatic changes in the present, past, and future.

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.

Multi-tracing of recharge seasonality and contamination in groundwater: A tool for urban water resource management.

In this study, sources of recharge and contamination in urban groundwater and in groundwater underneath a forest in the same aquifer were determined and compared. Data on hydro-chemical parameters and stable isotopes of water were collected in urban and forest springs in the Kharkiv region, Ukraine, over a period of 12 months. Groundwater transit time and precipitation contribution were calculated using hydrogeological data and stable isotopes of water to delineate groundwater recharge conditions. Hydro-chemical data, stable isotopes and emerging contaminants were used to trace anthropogenic groundwater recharge and approximate sewage and tap water contributions to the aquifer. The results indicated that each spring had unique isotopic signatures that could be explained by recharge conditions, groundwater residence time, and specific mixing patterns with sewage and water leaks. Elevated nitrate content, stable isotopes of nitrate, and the presence of emerging pollutants (mainly illicit drugs) in most of the urban springs confirmed mixing of urban groundwater with sewage leaks. These leaks amounted to up to 25% of total recharge and exhibited seasonal variations in some springs. Overall, the results show that urban groundwater receives variable seasonal contributions of anthropogenic components that increase the risk to the environment and human health, and reduce its usability for drinking water production. The multi-tracing approach presented can be useful for other cities worldwide that have similar problems of poor water management and inadequate sewage and water supply infrastructure.

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.

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.

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.