This study discusses the occurrence and environmental risk associated with a micropollutant plume originating from the direct discharge of treated wastewater into the Vidy Bay of Lake Geneva, Switzerland. The temporal variations and spatial extent of the plume and its effect on the presence of 39 pharmaceuticals and other micropollutants in the Vidy Bay were assessed over a 10 month period. A pronounced plume was observed from April to October, leading to locally elevated (up to 70-fold) pharmaceutical concentrations compared to the surrounding water column. For three of the measured substances, these plume-associated concentrations were sufficiently high to pose an ecotoxicological risk. The plume depth followed the thermal lake stratification, which moved to lower depths over the course of the warm seasons. Pharmaceutical hotspots associated with the plume were detected as far as 1.5 km downstream of the effluent wastewater outfall, but concentrations typically decreased with increasing distance from the wastewater outfall as a result of dilution and photodegradation. From November to January, when uniform temperature prevailed throughout the water column, no micropollutant plumes were detected. In contrast to pharmaceuticals, most pesticides showed homogeneous concentrations throughout the Vidy Bay during the whole study period, indicating that the effluent wastewater was not their dominant source. A strong linear correlation between electrical conductivity and concentrations of wastewater-derived micropollutants was identified. This relation will allow future estimates of wastewater-derived micropollutant concentrations via simple conductivity measurements.

Abstract. We introduce a new online global database of riverine water stable isotopes (Global Network of Isotopes in Rivers, GNIR) and evaluate its longer-term data holdings. Overall, 218 GNIR river stations were clustered into three different groups based on the seasonal variation in their isotopic composition, which was closely coupled to precipitation and snowmelt water runoff regimes. Sinusoidal fit functions revealed phases within each grouping and deviations from the sinusoidal functions revealed important river alterations or hydrological processes in these watersheds. The seasonal isotopic amplitude of δ 18 O in rivers averaged 2.5 ‰, and did not increase as a function of latitude, like it does for global precipitation. Low seasonal isotopic amplitudes in rivers suggest the prevalence of mixing and storage such as occurs via lakes, reservoirs, and groundwater. The application of a catchment-constrained regionalized cluster-based water isotope prediction model (CC-RCWIP) allowed for direct comparison between the expected isotopic compositions for the upstream catchment precipitation with the measured isotopic composition of river discharge at observation stations. The catchment-constrained model revealed a strong global isotopic correlation between average rainfall and river discharge (R 2 = 0.88) and the study demonstrated that the seasonal isotopic composition and variation of river water can be predicted. Deviations in data from model-predicted values suggest there are important natural or anthropogenic catchment processes like evaporation, damming, and water storage in the upstream catchment.

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Abstract. We introduce a new online global database of riverine water stable isotopes (Global Network of Isotopes in Rivers) and evaluate its longer-term data holdings. Overall, 218 GNIR river stations were clustered into 3 different groups based on the seasonal variation in their isotopic composition, which was closely coupled to precipitation and snow-melt water run-off regimes. Sinusoidal fit functions revealed periodic phases within each grouping and deviations from the sinusoidal functions revealed important river alterations or hydrological processes in these watersheds. The seasonal isotopic amplitude of δ18O in rivers averaged 2.5 ‰, and did not increase as a function of latitude, as it does for global precipitation. Low seasonal isotopic amplitudes in rivers suggest the prevalence of mixing and storage such as occurs via lakes, reservoirs, and groundwater. The application of a catchment-constrained regionalized cluster-based water isotope prediction model (CC-RCWIP) allowed direct comparison between the expected isotopic composition for the upstream catchment precipitation with the measured isotopic composition of river discharge at observation stations. The catchment-constrained model revealed a strong global isotopic correlation between average rainfall and river discharge (R2 = 0.88) and the study demonstrated that the seasonal isotopic composition and variation of river water can be predicted. Deviations in data from model predicted values suggest there are important natural or anthropogenic catchment processes, like evaporation, damming, and water storage in the upstream catchment.

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.

Waters were sampled monthly from a profile at the wastewater outlet and a reference point in the Bay of Vidy (Lake Geneva) for a year. The samples were analyzed for (18)O/(16)O of water, (13)C/(12)C of dissolved inorganic carbon (DIC), major ions, and selected micropollutant concentrations. δ(18)O values, combined with the major ion concentrations, allowed discharged waste and storm-drainage water to be traced within the water column. On the basis of δ(18)O values, mole fractions of wastewater (up to 45 %), storm-drainage (up to 16 %), and interflowing Rhône River water (up to 34 %) could be determined. The results suggest that the stormwater fractions do not influence micropollutant concentrations in a measurable way. In contrast, the Rhône River interflow coincides with elevated concentrations of Rhône River-derived micropollutants in some profiles. δ(13)C values of DIC suggest that an increase in micropollutant concentrations at the sediment-water interface could be related to remineralization processes or resuspension.

<p>Groundwater is the main source of drinking water in Slovenia, but nitrate pollution originating from agriculture and urban areas is threatening its quality in several areas of the country. The aim of this study is to assess the vulnerability of three different unconfined aquifers in Slovenia (Ljubljansko polje, Dravsko-ptujsko polje and Krško-brežiško polje). All three study areas are located on alluvial plains with shallow groundwater levels and similar soil types, but different ratios of urban and agricultural land use. Soil types and land use were analyzed in each area as they contribute strongly to leaching of nitrate. Along with this we performed the analysis of stable isotopes of O, H and N to determine the origin of groundwater recharge and trace the possible sources of nitrate pollution. Results will give us an overview of nitrate pollution pathways through better understanding of nitrate sources, vulnerable areas, and groundwater recharge characteristics.</p>

<p>Alluvial plains are an important agricultural area because of favourable soil properties, topography, and proximity to surface and groundwater resources. The predominant land use in the alluvial plains is agriculture, but there are also many urban and industrial areas. Groundwater bodies beneath the alluvial plains are threatened by nitrate pollution from agricultural activities and urban sources such as faulty sewage systems. For the Krško-Brežiško polje case study, an assessment of nitrate sources in groundwater was conducted using stable isotopes (<em>δ</em><sup>15</sup>N) to produce maps of groundwater vulnerability. In addition, stable isotope composition of groundwater (<em>δ</em><sup>18</sup>O and <em>δ</em><sup>2</sup>H) was used to obtain information on the characteristics of the recharge area. Nuclear techniques (i.e., stable isotopes) are excellent for determining pathways and travel times of contaminants through the vadose zone in soil-groundwater systems, especially in areas with shallow aquifers. Results show contamination from manure application and the potential to reduce pressures on groundwater for specific sampling points.</p><p>This research was financed by the ARRS L4-8221 URAVIVO and IAEA TCP SLO5004<strong> </strong>Improving Water Quality in Vulnerable and Shallow Aquifers under Two Intensive Fruit and Vegetable Production Zones.  </p>