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ZusammenfassungZwei Untersuchungsgebiete im zentralen Münsterland (Baumberge, NRW, Deutschland) sind aufgrund der geologischen Reliefumkehr-Situation isolierte Grundwasser-Ökosysteme, welche nur von infiltrierendem Niederschlagswasser beeinflusst werden. Als sogenannte „Natur-Lysimeter“ eignen sie sich mit ihren insgesamt bis zu 200 natürlichen Quellaustritten als multidisziplinäre Bezugssysteme für wasserdurchlässige Kluftgrundwasserleitersysteme (aus Kalkmergelsteinen). Die Betrachtung der langjährigen Veränderungen des Stoffaustrags an den Quellen deuten auf zunehmende Verkarstung und raumzeitlich wechselnde Einflüsse durch die land- und forstwirtschaftlich genutzte Geländeoberfläche hin. Stabile Sulfatisotope zeigen, dass die Mehrheit der Quellen durch den Eintrag von Gülle in deren Quell-Einzugsgebiet beeinflusst wird und dass die Pyritoxidation ein wichtiger Prozess im tieferen Grundwasserkörper ist. Die Nitratkonzentrationen sind im Allgemeinen hoch (über 50 mg/l) und stammen aus Gülle und/oder Kunstdünger, wie stabile Nitratisotope zeigen. Der ökologische Zustand des Grundwassersystems wird aufgrund von Crustaceen im Grundwasser als gut bewertet. Der Stoffaustrag jedes noch so kleinen Quellaustritts zeigt mit dem Grundwasserstand sich verändernde Zumischungsanteile von tieferem Grundwasser an.

Stable isotopes of water are ideal tracers to integrate into process‐based models, advancing ecohydrological understanding. Current tracer‐aided ecohydrological modeling is mostly conducted in relatively small‐scale catchments, due to limited tracer data availability and often highly damped stream isotope signals in larger catchments (>100 km2). Recent model developments have prioritized better spatial representation, offering new potential for advancing upscaling in tracer‐aided modeling. Here, we adapted the fully distributed EcH2O‐iso model to the Selke catchment (456 km2, Germany), incorporating monthly sampled isotopes from seven sites between 2012 and 2017. Parameter sensitivity analysis indicated that the information content of isotope data was generally complementary to discharge and more sensitive to runoff partitioning, soil water and energy dynamics. Multi‐criteria calibrations revealed that inclusion of isotopes could significantly improve discharge performance during validations and isotope simulations, resulting in more reasonable estimates of the seasonality of stream water ages. However, capturing isotopic signals of highly non‐linear near‐surface processes remained challenging for the upscaled model, but still allowed for plausible simulation of water ages reflecting non‐stationarity in transport and mixing. The detailed modeling also helped unravel spatio‐temporally varying patterns of water storage‐flux‐age interactions and their interplay under severe drought conditions. Embracing the upscaling challenges, this study demonstrated that even coarsely sampled isotope data can be of value in aiding ecohydrological modeling and consequent process representation in larger catchments. The derived innovative insights into ecohydrological functioning at scales commensurate with management decision making, are of particular importance for guiding science‐based measures for tackling environmental changes. Einstein Stiftung Berlin http://dx.doi.org/10.13039/501100006188 Berlin University Alliance http://dx.doi.org/10.13039/501100021727 Leverhulme Trust http://dx.doi.org/10.13039/501100000275

This study focuses on coastal aquifers subject to uncontrolled land use development by investigating the combined effects of seawater intrusion and nitrate contamination. The research is undertaken in a Mediterranean coastal agricultural area (Plain of the El-Nil River, Algeria), where water resources are heavily impacted by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ

Soluble reactive phosphorus (SRP) concentrations in agricultural headwaters can display pronounced seasonal variability at low flow, often with the highest concentrations occurring in summer. These SRP concentrations often exceed eutrophication levels, but their main sources, spatial distribution, and temporal dynamics are often unknown. The purpose of this study is therefore to differentiate between potential SRP losses and releases from soil drainage, anoxic riparian wetlands, and stream sediments in an agricultural headwater catchment. To identify the dominant SRP sources, we carried out three longitudinal stream sampling campaigns for SRP concentrations and fluxes. We used salt dilution tests and natural 222Rn to determine water fluxes in different sections of the stream, and we sampled for SRP, Fe, and 14C dissolved organic carbon (DOC) to examine possible redox-mediated mobilization from riparian wetlands and stream sediments. The results indicate that a single short section in the upper headwater reach was responsible for most of the SRP fluxes to the stream. Analysis of samples taken under summer low-flow conditions revealed that the stream water SRP concentrations, the fraction of SRP within total dissolved P (TDP), and DOC radiocarbon ages matched those in the groundwater entering the gaining section. Pore water from the stream sediment showed evidence of reductive mobilization of SRP, but the exchange fluxes were probably too small to contribute substantially to SRP stream concentrations. We also found no evidence that shallow flow paths from riparian wetlands contributed to the observed SRP loads in the stream. Combined, the results of this campaign and previous monitoring suggest that groundwater is the main long-term contributor of SRP at low flow, and agricultural phosphorus is largely buffered in the soil zone. We argue that the seasonal variation of SRP concentrations was mainly caused by variations in the proportion of groundwater present in the streamflow, which was highest during summer low-flow periods. Accurate knowledge of the various input pathways is important for choosing effective management measures in a given catchment, as it is also possible that observations of seasonal SRP dilution patterns stem from increased mobilization in riparian zones or from point sources.

Biogeochemical redox processes control the chemical behavior of many major and trace elements. Nitrogen is particularly sensitive to changes in soil redox conditions and its presence also affects the cycles of other redox-sensitive species, which causes its excessive application through agricultural fertilizers to be a multi-faceted problem.To assess these processes, we constructed a high-resolution monitoring station at an agricultural site featuring sensors and sampling facilities for analyzing hydraulics and hydrogeochemistry in the vadose zone and shallow groundwater. Monitoring has been performed for over two years during which different types of crops such as dill, spinach, wheat, and sunflower have been grown on the site. Observed variations of the oxidation-reduction potential over time and depth confirm the transient behavior of the redox reactive zone, whose variation is consistent with the fluctuation of the groundwater level. Also, a strong decrease in NO3- concentrations could be observed. This corresponds to changes over depthin both the sulfateconcentration and δ34S-SO42- signatures, whichconfirms the presence of autotrophic denitrification using sulfur as an electron donor. Moreover, a hydraulic model coupled with a heat transport model was set up for the estimation over depth of water fluxes, water content, and temperatures. In combination with the monitored concentrations, this allows us to estimate solute fluxes.Preliminary results indicate an average nitrate input to groundwater of 200 kg·ha-1·a-1, which is almost completely reduced in the shallow groundwater. However, at the same time, a production of only 25 kg·ha-1·a-1 of sulfate is estimated, which indicates that not only sulfur serves as an electron donor, and thus heterotrophic denitrification must also be taking place. This can be confirmed based on increased bicarbonate concentrations in the reactive zone. Furthermore, other nitrate-triggered redox processes were detected, including selenium accumulation at the redox interface, presumably resulting from seleno-pyrite-driven denitrification and geogenic uranium roll-front mobilization.

The riparian zone is a hydrologically and biogeochemically active zone, characterized by mixing of stream water with groundwater and transformation of nutrients such as nitrogen. The riparian zone thus plays a key role in natural attenuation of nitrate pollution. Among the attenuation processes in riparian zones, denitrification is the only one that leads to permanent removal of nitrogen from the riparian system via the release of dinitrogen gas into the atmosphere. In contrast, other biogeochemical processes such as nitrate uptake by plants merely result in a temporary nitrogen retention within riparian zones. While hydrochemical data and endmember modelling can help assess nitrate transformation in riparian aquifers, this does not allow quantifying the extent of nitrate removal via denitrification. In this talk, I will demonstrate how nitrate isotope data can be used in combination with chloride and nitrate concentration data to quantify spatial and temporal variations in the extent of denitrification and mixing between groundwater and surface water. I will illustrate how the application of this approach to a riparian groundwater study site in Central Germany revealed that denitrification is largely exceeded by other processes that merely lead to temporary nitrate removal from the riparian groundwater. In comparable settings, a major fraction of nitrogen inputs is thus likely retained in riparian zones and may eventually be discharged into rivers. Such information is crucial to determine the effectiveness of riparian zones for removing nitrate from aquatic ecosystems, which is highly relevant for many river ecosystems at risk of eutrophication because of high nitrogen inputs from agriculture.ReferenceLutz, S. R., Trauth, N., Musolff, A., Van Breukelen, B. M., Knöller, K., & Fleckenstein, J. H. (2020). How important is denitrification in riparian zones? Combining end-member mixing and isotope modeling to quantify nitrate removal from riparian groundwater. Water Resources Research, 56, e2019WR025528. https://doi.org/10.1029/2019WR025528

Nitrification and denitrification are traditionally assumed to occur under aerobic and anoxic conditions, respectively. However, new and interesting alternatives challenge the traditional assumption. Along this line, we provide dual-nitrate isotopic and chemical evidence for the occurrence of denitrification linked with heterotrophic nitrification in an upper oxic region and nitrification in an underlying low-oxygen (sub-oxic/anoxic) layer of a stratified and channelized alluvial aquifer. Particularly significant is the source of the oxidant required for nitrification within the deeper low-oxygen layer. Combined with the existence of steep geochemical gradients, the introduction of a favorable manganese oxide oxidant from the upper oxic layer into the underlying low oxygen region during diffusive mixing resulted in the higher concentrations of nitrate observed (due to the anoxic reoxidation of nitrite to nitrate) as well as the strong positive correlation of nitrite/nitrate with manganese (II) ion concentrations (in the deeper anoxic layer compared with the shallower oxic layer). The observations and findings presented herein have implications for not only reconciling the discrepancies in such unconventional pathways of nitrogen metabolism between groundwater ecosystems and river/stream/soil/marine systems (where such processes have most commonly been reported) but also for devising effective nitrogen nutrient remediation and complex nitrogen-cycling modeling strategies.

The control of macroalgal bloom development is central for protecting estuarine ecosystems. The identification of the nutrients limiting the development of macroalgal blooms, and their most likely sources is crucial for management strategies. Three Irish estuaries (Argideen, Clonakilty and Tolka) affected by green tides were monitored from June 2016 to August 2017. During each sampling occasion, biomass abundances, tissue N and P contents, and delta15N were determined for tubular and laminar morphologies of Ulva. All estuaries showed maximum biomass during summer and minimum during winter. Tissue nutrient contents revealed P rather than N limitation. The delta15N during the peak bloom indicated agriculture as the most likely source of nitrogen in the Argideen and Clonakilty, and urban wastewaters in the Tolka. No differences in the delta15N, and the tissue nutrients content were observed between morphologies. The period between May and July is most suitable for bioassessment of green tides., This work has been co-financed under the 2014-2020 EPA Research Strategy (Environmental Protection Agency, Ireland), project no: 2015- W-MS-20 (the Sea-MAT Project) and project no: 2018-W-MS-32 (the MACRO-MAN Project), and the 2014-2020 ERDF Operational Programme and by the Department of Economy, Knowledge, Business and University of the Regional Government of Andalusia (Project reference: FEDER-UCA18-106875). The authors are thankful to Moya O’Donnell, Maria Galindo-Ponce, Claudia Cara-Ortega, Micheal Mac Monagail, Ana Mendes, Charlene Linderhof, Nichole Keogh, Andrew Niven and Edna Curley for field assistance and Robert Wilkes for advice.

Nitrate monitoring is commonly conducted with low‐spatial resolution, only at the outlet or at a small number of selected locations. As a result, the information about spatial variations in nitrate export and its drivers is scarce. In this study, we present results of high‐spatial resolution monitoring conducted between 2012 and 2017 in 65 sub‐catchments in an Alpine mesoscale river catchment characterized by a land‐use gradient. We combined stable isotope techniques with Bayesian mixing models and geostatistical methods to investigate nitrate export and its main drivers, namely, microbial N turnover processes, land use and hydrological conditions. In the investigated sub‐catchments, mean values of NO3− concentrations and its isotope signatures (δ15NNO3 and δ18ONO3) varied from 2.6 to 26.7 mg L−1, from −1.3‰ to 13.1‰, and from −0.4‰ to 10.1‰, respectively. In this study, land use was an important driver for nitrate export. Very strong and strong positive correlations were found between percentages of agricultural land cover and δ15NNO3, and NO3− concentration, respectively. Mean proportional contributions of NO3− sources varied spatially and seasonally, and followed land‐use patterns. The mean contribution of manure and sewage was much higher in the catchments characterized by a high percentage of agricultural and urban land cover comparing to forested sub‐catchments. Specific NO3− loads were strongly correlated with specific discharge and moderately correlated with NO3− concentrations. The nitrate isotope and concentration analysis results suggest that nitrate from external sources is stored and accumulated in soil storage pools. Nitrification of reduced nitrogen species in those pools plays the most important role for the N‐dynamics in the Erlauf river catchment. Consequently, nitrification of reduced N sources was the main nitrate source except for a number of sub‐catchments dominated by agricultural land use. In the Erlauf catchment, denitrification plays only a minor role in controlling NO3− export on a regional scale., We integrated results of the BMM with informative priors and top‐kriging. Reduced N stored in soil is an important source for stream N in a mesoscale catchment. Manure and sewage is the main NO3− source in agricultural sub‐catchments. Denitrification played only a minor role in controlling regional scale NO3− export.

Implementing sustainable groundwater resources management in coastal areas is challenging due to the negative impacts of anthropogenic stressors and various interactions between groundwater and surface water. This study focuses on nitrate contamination and transport via groundwater-surface water exchange in a Mediterranean coastal area (Guerbes-Senhadja region, Algeria) that is heavily affected by anthropogenic activities. A multi-tracer approach, integrating hydrogeochemical and isotopic tracers (δ

Rationale: A silver phosphate reference material (Ag3PO4) for the measurement of stable oxygen isotope compositions is much needed; however, it is not available from the authorities distributing reference materials. This study aims to fill this gap by calibrating a new Ag3PO4 stable isotope comparison material produced by the University of Natural Resources and Life Sciences (BOKU).Methods: Aliquots of Ag3PO4 were distributed to four laboratories who frequently measure the δ18O value in Ag3PO4 ; the University of Natural Resources and Life Sciences (BOKU), the University of Western Australia (UWA), the University of Helsinki (UH), and the Helmholtz Centre for Environmental Research (UFZ). The instruments used to perform the measurements were high-temperature conversion elemental analysers coupled with continuous flow isotope ratio mass spectrometers. The working gas δ18O value was set to 0‰ and the normalization was done by a three-point linear regression using the reference materials IAEA-601, IAEA-602, and NBS127.Results: The mean δ18O value of the new BOKU Ag3PO4 comparison material on the VSMOW-SLAP scale is 13.71‰ and the combined uncertainty is estimated as ±0.34‰. This estimated uncertainty is within the range typical for comparison materials of phosphates and sulphates. Consistent results from the different laboratories probably derived from similar instrumentation, and use of the same reference materials and normalization procedure. The matrix effect of the different reference materials used in this study was deemed negligible. Conclusions: The BOKU Ag3PO4 can be used as an alternative comparison material for stable oxygen isotope analysis and is available for stable isotope research laboratories to facilitate calibration. published

Low order streams drain a big proportion of river catchments. They are not only fed by groundwater, but may also lose water to their connected aquifers and, in turn, can contribute to a substantial fraction of groundwater recharge. In such cases, these streams are typically characterized by the coexistence of gaining and losing stream reaches. Along the bidirectional exchange flow paths large biogeochemical gradients can evolve so that the exchange zones can function as hotspots for biogeochemical processes (such as the important (de)nitrification processes in croplands), which can substantially change under these two conditions. An agricultural first order stream (Schönbrunnen) in south-western Germany was equipped with stream gauging stations and piezometers were installed in the adjacent shallow aquifer, in order to find out how these biogeochemical processes change under losing versus gaining conditions. Hydrological and hydrochemical variables within the immediate vicinity of the stream, as well as stable nitrogen isotopes have been monitored between August 2017 and May 2020 to spatially and temporally identify the controls of nitrogen cycling dynamics in the Schönbrunnen.Gaining and losing conditions at the Schönbrunnen were determined by salt tracer experiments and the flow direction (upwelling groundwater or downwelling streamwater) of the exchanging fluxes was determined based on hydraulic head contour maps.Hydrochemical data suggests that nitrate reduction occurs within the first 20 cm of the streambed in the losing reaches. In these reaches, isotopic data depicts that nitrate is reduced along the flow path between stream and groundwater. Ammonium and organic electron donors (DOC) were found at greater depths in these reaches. By contrast, increasing nitrite and nitrate concentrations were observed also along the last 20 cm of the upwelling flow paths (gaining reaches). In summary, assuming that the transition zone between groundwater and streams is only a hotspot for denitrification might not always be true, as our field data suggests that redox conditions in the streambed, and in turn, the resulting biogeochemical processes differed substantially between losing and gaining reaches.

The science of the total environment 769, 144324 (2021). doi:10.1016/j.scitotenv.2020.144324, Published by Elsevier Science, Amsterdam [u.a.]

Information about groundwater residence times is essential for sustainable groundwater management. Naturally occurring radionuclides are suitable tools for related investigations. While the applicability of several long-lived radionuclides has been demonstrated for the investigation of long residence times (i.e., years, decades, centuries and more), studies that focus on sub-yearly residence times are only scarcely discussed in the literature. This shortage is mainly due to the rather small number of radionuclides that are generally suitable for the purpose and show at the same time adequately short half-lives. A promising innovative approach in this regard applies cosmogenic radiosulfur (35S). 35S is continuously produced in the stratosphere from where it is conveyed to the troposphere or lower atmosphere and finally transferred with the rain to the groundwater. As soon as the meteoric water enters the subsurface, its 35S activity decreases with an 87.4 day half-life, making 35S a suitable time tracer for investigating sub-yearly groundwater ages. However, since precipitation shows a varying 35S activity during the year, setting up a reliable 35S input function is required for sound data evaluation. That calls for (i) an investigation of the long-term variation of the 35S activity in the rain, (ii) the identification of the associated drivers and (iii) an approach for setting up a 35S input function based on easily attainable proxies. The paper discusses 35S activities in the rain recorded over a 12-month period, identifies natural and anthropogenic influences, and suggests an approach for setting up a 35S input function applying 7Be as a proxy.

A silver phosphate comparison material (Ag3PO4) for measurement of the stable oxygen isotope composition was prepared by the University of Natural Resources and Life Science (BOKU) and distributed to four international isotope laboratories frequently measuring the δ18O value in Ag3PO4. The contributing laboratories were the University of Natural Resources and Life Science (BOKU), The University of Western Australia (UWA), the ETH Zurich (ETH), the University of Helsinki (UH) and the Helmholtz Centre for Environmental Research (UFZ). Each laboratory analysed the comparison material in a minimum of two independent measuring rounds with a minimum of 10 individual measurements. The instrument used to perform the measurements were high-temperature conversion elemental analyzers coupled with continuous flow isotope ratio mass spectrometers: TC/EA with Thermo Finnigan Delta XP (BOKU), a TC/EA with a Thermo Scientific Delta V Plus (UWA), an Elementar Pyrocube with a Isoprime 100 (ETH), a Flash IRMS EA with a Thermo Scientific Delta V Plus (UH) and a TC/EA with a Finnigan Delta S (UFZ). The working gas δ18O was set to 0 ‰ and the normalization was done by a three-point linear regression calibration (Paul et al., 2007) using the reference material IAEA-601 (δ18OVSMOW = +23.14 ± 0.17 ‰), IAEA-602 (δ18OVSMOW = +71.28 ±0.42 ‰) (both benzoic acid) and NBS 127 (barium sulfate) (δ18OVSMOW = +8.59 ± 0.20 ‰) (Brand et al., 2009). BOKU, UH and ETH had experienced inhomogeneity of the IAEA-602 as already mentioned in Brand et al. (2009). The weighted arithmetic mean and standard deviation (1σ) of the new BOKU Ag3PO4 comparison material from the single measurements has a δ18O value of 13.80 ± 0.40 ‰ on the VSMOW scale (n=131), while the median of the single rounds was 13.76 ‰ (n=11) and the median of the laboratories was 13.79 ‰ (n=5). The arithmetic means of two measuring rounds were outside ± 1σ. When excluding data from these rounds from the statistics the weighted arithmetic mean has a δ18O value of 13.80 ± 0.32 ‰ on the VSMOW scale (n = 111) and the median of the single valid rounds (n=9) remained at 13.76 ‰ and the median of the labs at 13.79 ‰ (n=5). Excluding NBS127 from the normalization slightly reduced the δ18O value to 13.74 ± 0.31 ‰ (n = 111). The BOKU Ag3PO4 comparison material is available for stable isotope research laboratories to facilitate the calibration of their lab comparison material. Brand, W.A., Coplen, T.B., Aerts-Bijma, A.T., Böhlke, J.K., Gehre, M., Geilmann, H., Gröning, M., Jansen, H.G., Meijer, H.A.J., Mroczkowski, S.J., Qi, H., Soergel, K., Stuart-Williams, H., Weise, S.M., Werner, R.A., 2009. Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques. Rapid Communications in Mass Spectrometry, 999–1009. doi:10.1002/rcmPaul, D., Skrzypek, G., Fórizs, I., 2007. Normalization of measured stable isotopic compositions to isotope reference scales - A review. Rapid Communications in Mass Spectrometry 21, 3006–3014. doi:10.1002/rcm.3185

The eutrophic lake Eichbaumsee, a ~ 1 km long and 280m wide (maximum water depth 16m) dredging lake southeast of Hamburg (Germany), has been treated for water quality improvements using various techniques (i.e. aeration plants, removal of dissolved phosphate by aluminium phosphate precipitation and by Benthophos adsorption) during the past ~ 15 years. Despite these treatments no long-term improvement of the water quality was observed and the lake water phosphate content continued to increase by e.g. ~ 350 kg phosphate per year between March 2016 and February 2019. As no creeks or rivers drain into the lake and hydrological groundwater models do not suggest any major groundwater discharge into the lake, sources of phosphate (and other nutrients) are unknown.We investigated the phosphate fluxes from sediment pore water and groundwater into the water body of the lake. Sediment pore water was extracted from sediment cores recovered by divers in August 2018 and February 2019. Diffusive phosphate fluxes from pore water were calculated based on phosphate gradients using first Fick`s law. Stable water isotopes (δ2H, δ18O) were measured in the lake water, sediment pore water, interstitial waters in the banks surrounding the lake, the Elbe river and in three groundwater wells close to lake. Stable isotope (δ2H, δ18O) water mass balance models were used to compute water inflow/outflow to/from the lake.Our results revealed pore-water borne phosphate fluxes between – 0.07 mg/m²/d (i.e. slight phosphate uptake by the sediments) and 2.6 mg/m²/d (i.e. phosphate release to the lake). Assuming that the measured phosphate fluxes are temporarily and spatially representative for the whole lake, about 100 kg/a to 220 kg/a of phosphate is released from sediments. This amount is slightly lower than the observed phosphate increase of the lake water. Stable isotope signatures indicate a water exchange between the aquifer and the lake water. Based on stable isotope mass balances (δ2H, δ18O) we estimate an inflow of phosphate from the aquifer to the lake between 190 kg/a and 1400 kg/a. This inflow indicates that groundwater-born phosphate is as or even more important than phosphate supply via sediment pore-water. Our study suggests that groundwater may have an important impact on lake nutrient budgets.

The water composition of the river Adige displays a Ca&ndash, HCO3 hydrochemical facies, mainly due to rock weathering. Nitrate is the only component that has increased in relation to growing anthropogenic inputs. The aim of this paper was to identify the origin of the dissolved components in this river and to establish the relationship between these components and critical zone processes within an evolving framework where climatic and human impacts are influencing the riverine system. In particular, emphasis is given to a wide spectrum of isotope data (&delta, 18O, &delta, 2H, &delta, 13C, &delta, 15N, &delta, 34S, 87Sr/86Sr, &delta, 11B), which is considered useful for determining water origin as well as natural and anthropogenic impacts on riverine geochemistry. Together with oxygen and hydrogen isotopes, which are strictly related to the climatic conditions (precipitation, temperature, humidity), the carbon, sulphur, strontium and boron signatures can describe the magnitude of rock weathering, which is in turn linked to the climatic parameters. &delta, 13CDIC varies regularly along the riverine profile between &minus, 4.5&permil, and &minus, 9.5&permil, and &delta, 34SSO4 varies regularly between +4.4&permil, and +11.4&permil, On the other hand, &delta, 15NNO3 shows a more scattered distribution between +3.9&permil, and +10.5&permil, with sharp variations along the riverine profile. 87Sr/86Sr varies between 0.72797 in the upper part of the catchment and 0.71068 in the lower part. &delta, 11B also shows a rough trend, with values approaching 7.6&permil, in the upper part and 8.5&permil, in the lower part. In our view, the comparatively low &delta, 34S, &delta, 11B, and high 87Sr/86Sr values, could be a proxy for increasing silicate weathering, which is a process that is sensitive to increases in temperature.

Riparian zones are important buffer zones for streams as they are hotspots of nitrate transformation and removal in agricultural catchments. However, mixing of water from different sources and various transformation processes can complicate the quantification of nitrate turnover in riparian zones. In this study, we analyzed nitrate concentration and isotope data in riparian groundwater along a 2-km stream section in central Germany. We developed a mathematical model combining end-member mixing and isotope modeling to account for mixing of river water and groundwater and quantify nitrate transformation in riparian groundwater. This enabled us to explicitly determine the extent of denitrification (as process leading to permanent nitrate removal from riparian groundwater) and transient nitrate removal by additional processes associated with negligible isotope fractionation (e.g., plant uptake and microbial assimilation) and to perform an extensive uncertainty analysis. Based on the nitrogen isotope data of nitrate, the simulations suggest a mean removal of up to 28% by additional processes and only about 9% by denitrification. Nitrate removal from riparian groundwater by additional processes exceeded denitrification particularly in winter and at larger distance from the river, underlining the role of the river as organic carbon source. This highlights that nitrate consumption by additional processes predominates at the field site, implying that a substantial fraction of agricultural nitrogen input is not permanently removed but rather retained in the riparian zone. Overall, our model represents a useful tool to better compare nitrogen retention to permanent nitrogen removal in riparian zones at various temporal and spatial scales.

As more regions in the world look to replenish depleted aquifers, treated wastewater (TWW) is increasingly infiltrated in managed aquifer recharge (MAR) schemes. While MAR is a promising emerging technology, it also has the potential to generate pollutants along the infiltration flow path. In this study, we infiltrated treated wastewater through an organic-rich soil in column experiments operated with wetting and drying cycles. Ammonium, which was present only in trace concentrations in the TWW, increased in concentration with depth and exceeded the EU Water Framework Directive limit of 0.5 mg/L for up to a year, depending on the sampling depth. Pore water samples collected at the end of drying periods showed very high nitrate concentrations, indicating nitrification of some of the ammonium. Oxidation reduction potential often exceeded 200 mV during drying periods, showing conditions for nitrification, but dropped below −100 mV during wetting periods, creating several possible pathways for ammonium production. Potential sources of ammonium are (1) dissolved organic nitrogen in the TWW, (2) nitrate in the TWW, and (3) organic nitrogen in the soil. δ15N in ammonium in pore water samples (mean 4.7‰) was slightly higher than δ15N in the soil (2.4‰), indicating that the soil was likely the major source but also that nitrate (mean 17.2‰) may have been the source of some of the ammonium. Fractionation of 15N in nitrate as well as high concentrations of acetate (a labile organic carbon source) also indicate that dissimilatory nitrate reduction to ammonium may have formed some of the NH4+.

The red seaweed Agarophyton vermiculophyllum is an invasive species native to the north-west Pacific, which has proliferated in temperate estuaries of Europe, North America and Africa. Combining molecular identification tools, historical satellite imagery and one-year seasonal monitoring of biomass and environmental conditions, the presence of A. vermiculophyllum was confirmed, and the invasion was assessed and reconstructed. The analysis of satellite imagery identified the first bloom in 2014 and revealed that A. vermiculophyllum is capable of thriving in areas, where native bloom-forming species cannot, increasing the size of blooms (ca. 10%). The high biomass found during the peak bloom (>2 kg m−2) and the observation of anoxic events indicated deleterious effects. The monitoring of environmental conditions and biomass variability suggests an essential role of light, temperature and phosphorous in bloom development. The introduction of this species could be considered a threat for local biodiversity and ecosystem functioning in a global change context.

Since 2014, reclaimed water has been used for agricultural irrigation and it has been discharged on a riverbed of the Maneadero aquifer, Baja California, Mexico. To determine the effects of reclaimed water on groundwater quality, samples of reclaimed water and groundwater were collected spatiotemporal and analyzed using stable isotope (δ18OH2O, δ2HH2O, δ18ONO3 and δ15NNO3) and geochemical signatures, jointly with multivariate statistical methods and a 2D resistivity tomography. Reverse ion exchange and mineralization are the main processes influencing the groundwater composition. The Cl/Br ratios identified seawater intrusion and solid waste, wastewater and animal waste as the main sources responsible for these processes, overlapping with the ratios of reclaimed water. Nitrates are pervasive throughout the aquifer and δ18ONO3 and δ15NNO3 attributed wastewater and animal waste as the major nitrates inputs. Multivariate statistics were able to separate seawater and human-derived processes. The δ18OH2O and δ2HH2Oshowed the effect of mixing with d-excess of 5–6‰, indicating recharge other than precipitation. A mixing model using Cl− and δ18OH2O and principal components revealed the mixing proportion of seawater; whilst the over- and under-estimates of reclaimed water contribution are indicative of missing end-members. The Na-Cl-Br-B systematics, however, suggest that reclaimed water result in cation-exchange and adsorption reactions and once the adsorbed sites become saturated with respect of Na+, Br−and B−can be reflected in the groundwater composition. Additionally, resistivities indicate that reclaimed water interacts between the fresh and brackish groundwater. Monitoring the efficiency of the vadose zone to retain contaminants and distinguish them from reclaimed water is essential for evaluating groundwater quality.

Standard sulfur isotope analysis of aqueous samples is aimed at sulfide and sulfate, while often disregarding intermediate species, mainly due to analytical limitations. However, sulfur can form numerous intermediate species in the environment, including thiometal(loid)s such as thioarsenates ([HAsVS− IInO4 − n]2 −, n = 1–4), which can play a key role in isotope fractionation. The standard precipitation procedure for separation of sulfide and sulfate was applied to monothioarsenate solutions. Monothioarsenate was found to co-precipitate together with sulfide, thus potentially impeding correct sulfide isotope analysis. To overcome the limitations associated with this standard precipitation procedure, a new method was developed based on separating sulfur species by ion chromatography followed by online isotope detection on multi-collector ICP-MS (IC-MC-ICP-MS). Applying this new method, fractionation between monothioarsenate and sulfate of up to − 6.1‰ was found during monothioarsenate oxidation. In contrast, oxidation of tetrathioarsenate via tri- and di- to monothioarsenate did not result in fractionation. However, the released sulfide became increasingly enriched in 34S due to oxidation to sulfate. This process was found to introduce additional enrichment of up to 9.1‰ to monothioarsenate through intermolecular isotope exchange between arsenic-bound sulfur and sulfide in solution. These results help elucidate pathways of thioarsenate transformation, and thus provide valuable information for the interpretation of isotope fractionation patterns in sulfidic environments.

Cosmogenic radiosulfur (35S; half-life: 87.4 days) is transferred with the rain to the groundwater (as 35SO42−) and can be used as residence time tracer for the detection of sub-yearly groundwater residence times. Due to the distinct but non-regular annual 35S pattern in precipitation, related data evaluation requires consideration of a35S input function that is based on representative rain samples. While minor rain events can easily be sampled quantitatively and hence representatively, a long-lasting rain event may get documented by a sample that represents only a certain sequence of the event, thus potentially resulting in a35S activity concentration that might not be representative. With the aim to examine the magnitude of temporal variations of the 35S activity concentration in rain during long-lasting rain events, we present and discuss two related exemplary 35S time series. Furthermore, we evaluate the applicability of the parameters total sulfate and electrical conductivity (EC), both detected in rainwater as easily attainable 35S proxies. The results of the study show (i) that the 35S activity concentration may vary substantially during long-lasting rain events due to atmospheric migration processes and aerosol washout and (ii) that neither sulfate nor EC are suitable as 35S proxies due to the different origin of 35S on the one hand and sulfate/EC on the other. Hence, for the determination of a35S activity concentration that is representative for a long-lasting rain event 35S analyses of an adequate number of sub-samples cannot be avoided.

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.

Natural attenuation processes depend on the availability of suitable electron acceptors. At the megasite Zeitz, concentrations of the main contaminant benzene were observed to increase constantly in the lower aquifer to levels of more than 2.5 mM. This was accompanied by decreasing concentrations of sulphate (SO42−), which has been previously shown to be the main electron acceptor for benzene oxidation at this site, resulting in an electron acceptor-limited, sulphidic benzene plume. Therefore, a field experiment was conducted to stimulate benzene biodegradation by injecting nitrate (NO3−) into the sulphidic benzene plume aiming (i) to recycle sulphate by nitrate-dependent sulphide oxidation, and (ii) to serve as direct electron acceptor for benzene oxidation. Within 60 days, 6.74 tons sodium nitrate (NaNO3) were injected into the lower aquifer, and the resulting biogeochemical effects within the benzene plume were monitored for more than one year by chemical and microbiological analyses of groundwater samples taken from various depths of ten monitoring wells located in three observation lines downstream of nitrate injection. Nitrate was microbiologically consumed, as shown by changes in δ15N-NO3− and δ18O-NO3− values, partial nitrite accumulation, and changing ratios of Na+/NO3−. Main electron donors for nitrate reduction were reduced sulphur compounds, verified by changing δ34S-SO42− and δ18O-SO42− values, partially increasing sulphate concentrations, and strongly increasing abundances of typical sulphur-oxidizing, nitrate-reducing bacterial taxa within the nitrate plume. The general absent hydrogen isotope fractionation of benzene, also in the sulphidic, nitrate-free part of the plume, indicates that benzene was not biodegraded by sulphate-reducing consortia. However, detected small carbon isotope fractionation of benzene points to in situ benzene biodegradation processes in the plume, probably supported by nitrate. In conclusion, nitrate injection resulted in changing redox conditions and recycling of sulphate in the sulphidic, sulphate-depleted benzene plume due to microbial oxidation of reduced sulphur species, leading to presumably favored conditions for in situ benzene biodegradation.

Nitrate loads and corresponding dual-isotope signatures were used to evaluate large scale N dynamics and trends in a river catchment with a strong anthropogenic gradient (forest conservation areas in mountain regions, and intensive agriculturally used lowlands). The Bode River catchment with an area of 3200 km(2) in the Harz Mountains and central German lowlands was investigated by a two years monitoring program including 133 water sampling points each representing a subcatchment. Based on discharge data either observed or simulated by the mesoscale hydrological model (mHM) a load based interpretation of hydrochemical and isotope data was conducted. Nitrate isotopic signatures in the entire catchment are influenced by (I) the contribution of different nitrogen sources, (II) by variable environmental conditions during the formation of nitrate, and (III) by a minor impact of denitrification. For major tributaries, a relationship between discharge and nitrate isotopic signatures is observed. This may in part be due to the fact, that during periods of higher hydrologic activity a higher wash out of isotopically lighter nitrate formed by bacterial nitrification processes of reduced or organic soil nitrogen occurs. Beyond that, in-stream denitrification seems to be more intense during periods of low flow.

The present study investigated lake and river sediments affected by metals from an acid mine drainage (AMD) from a former uranium mine. The role of bacterial sulfate reduction in the immobilization of contaminants was evaluated, and the analyses of acid volatile sulfide (AVS) and sequential extraction were performed. Consequently, the potential mobility and bioavailability of contaminants were established. Sulfur isotopic fractionation (δ34S), AVS, and sequential extraction procedure were used to assess the sulfate bacterial reduction and the availability of contaminants in the environment at six sampling stations. The δ34S indicated that bacterial reduction is a key process in the natural attenuation of contamination in the Aguas Claras reservoir, precipitating metal sulfides. According to the USEPA criteria, adverse biological effects are expected for sample S1 (inside the reservoir) which is likely to be toxic, while for sediment S4 (in the river), the toxicity is uncertain. The other samples were classified as non-toxic, likely because of the decreased solubility of zinc sulfide. A decrease in the concentration of the contaminants downstream of the reservoir was observed. The predominance of U (0.4 %) in the labile fraction and the elevated concentrations of Zn (0.5 %) and Mn (0.7 %) in the sediments inside the reservoir raises concerns regarding the availability of these contaminants in the environment. The main environmental impact appears to be concentrated in the Aguas Claras reservoir, whereas the Antas creek does not seem to be affected by the AMD process. Although the bacterial sulfate reduction is effective in its production of sulfides capable of immobilizing the contaminants, the presence of Zn and U in the labile and reducible fraction is a matter of concern due to its long-term bioavailability. Thus, continuous monitoring of the redox potential of the waters and sediments, mainly in the reservoir, is recommended in order to assess and possibly prevent later dissolution of sequestered contaminants.

Mikrobiologische Abbauprozesse tragen masgeblich zur Minderung der Nitratbelastung in sedimentaren Grundwasserleitern bei, indem Nitrat unter Verbrauch von organischem Kohlenstoff (heterotroph) und Eisensulfiden bspw. Pyrit (autotroph) reduziert wird. Allerdings sind diese Phasen in Sedimenten oft nur in Spuren vorhanden und werden im Verlauf der Reaktionen aufgebraucht, sodass der Nitratabbau zum Erliegen kommen konnte. Um Masnahmen im Zuge der EG-Wasserrahmenrichtlinie umsetzen zu konnen, wurden das Nitratabbaupotenzial und die Abbauprozesse in den z. T. stark nitratbelasteten Grundwasserleitern des Hessischen Rieds untersucht. Das Abbaupotenzial wurde an Bohrkernproben mittels Festphasenanalytik quantifiziert und charakterisiert. Mit tiefenorientierter Untersuchung der Hydrochemie (u. a. stabile Isotope und N2Exzess) konnten Nitrateintrage, Abbaufortschritt und Abbauprozesse sowie durchschnittliche Abbauraten im Anstrom ausgewahlter Grundwassermessstellen bestimmt werden. Trotz geringer Sulfidgehalte (max. 123 mg-S/kg) konnte oft ein dominant autotropher Nitratabbau nachgewiesen werden. Die Ergebnisse dieser Studie dienen der Ausweisung von Risikogebieten, in deren Abstrom in naher Zukunft, bei gleichbleibend hohen Nitrateintragen, mit nachlassendem Nitratabbau gerechnet werden muss.

Nitrogen fate and transport through contaminated groundwater systems, where N is both ubiquitous and commonly limits pollutant attenuation, must be re-evaluated given evidence for new potential microbial N pathways. We addressed this by measuring the isotopic composition of dissolved inorganic N (DIN = NH4+, NO2−, and NO3−) and N functional gene abundances (amoA, nirK, nirS, hszA) from 20 to 38 wells across an NH4+, hydrocarbon, and SO42− contaminated aquifer. In-situ N attenuation was confirmed on three sampling dates (0, +6, +12 months) by the decreased [DIN] (4300 - 40 μM) and increased δ15N-DIN (5‰–33‰) over the flow path. However, the assumption of negligible N attenuation within the plume was complicated by the presence of alternative electron acceptors (SO42−, Fe3+), both oxidizing and reducing functional genes, and N oxides within this anoxic zone. Active plume N cycling was corroborated using an NO2− dual isotope based model, which found the fastest (∼10 day) NO2− turnover within the N and electron donor rich central plume. Findings suggest that N cycling is not always O2 limited within chemically complex contaminated aquifers, though this cycling may recycle the N species rather than attenuate N.

To study the significance of land use and catchment hydrology for the age of exported carbon, we measured the radiocarbon abundances in two mountainous streams in Germany. The Hassel catchment was characterized by wider-stretched riparian areas and by a significant contribution of arable land and pasture to land use compared to the Rappbode catchment. Although soil cultivation is considered to mobilize old carbon from deep soil layers, in six out of eight situations dissolved organic carbon (DOC) was younger in Hassel stream compared to Rappbode. In contrast, we estimated annual exports of radiocarbon on the basis of yield weighed, bulked biweekly samples and found that older DOC was delivered from Hassel compared to Rappbode catchment (352 years conventional radiocarbon age as well as carbon near to modern origin, respectively). This result characterized primarily the fluxes during wet conditions, which dominated the annual exports. In a winter base flow situation, we found that old (~2550 years) snow-bound organic carbon deriving from atmospheric deposition contributed 29–43 % to stream exports. Overall, there was significant intra-annual variability of stream 14C-DOC. Within the catchments, the standard deviations of ∆14C values (47–63 ‰) were comparable to the difference of annual exports between the contrasting catchments (46 ‰). Infrequent storm flow events should be included not only in export budgets but also in studies of carbon sources.

Only limited data on the isotopic and chemical composition of Riyadh rain are currently available. In this study, we complement these data by analyzing integral samples covering 28 precipitation events between 2009 and 2013. Results of stable isotope analyses are used to establish a Local Meteoric Water Line: δ 2 H = 5.22(± 0.38) · δ 18 O + 14.8(± 0.9) ‰. Moisture source-related isotopic fingerprints are masked by the continental effect, the altitude effect, sub-cloud evaporation, and moisture recycling. The study of one event for intra-storm variability revealed strong isotopic depletion due to rainout and Rayleigh distillation processes, thus highlighting the general need for integral samples. Tritium analyses of grab samples from 12 events yielded concentrations between 2.8 and 6.4 tritium units (TU), which are close to the natural background of a few TU. Major ion concentrations and ratios indicate that solutes are predominantly derived from atmospheric dust originating from limestone outcrops and sabkha deposits. The latter play a role with respect to the elevated Cl − and Na + contents, but are probably also responsible for the SO 4 2 − and a part of the Ca 2 + found in Riyadh rain. Observed intra- and inter-storm variabilities of major ion levels necessitate the collection of integral samples and the calculation of precipitation-weighted means, respectively. The obtained isotopic signatures and the precipitation-weighted mean Cl − concentration (9.5 mg L − 1 ) may be useful in groundwater assessments, e.g., for the identification of modern recharge and quantification thereof by means of the Chloride Mass Balance method.

Summary Groundwater is one of the main resources for drinking water. Its quality is still threatened by the widespread contaminant nitrate (NO3−). In order to manage groundwater resources in a sustainable manner, we need to find options of lowering nitrate input. Particularly, a comprehensive knowledge of nitrate sources is required in areas which are important current and future drinking water reservoirs such as pre-alpine aquifers covered with permanent grassland. The objective of the present study was to identify major sources of nitrate in groundwater with low mean nitrate concentrations (8 ± 2 mg/L). To achieve the objective, we used environmental tracer approaches in four pre-alpine groundwater catchments. The stable isotope composition and tritium content of water were used to study the hydrogeology and transit times. Furthermore, nitrate stable isotope methods were applied to trace nitrogen from its sources to groundwater. The results of the nitrate isotope analysis showed that groundwater nitrate was derived from nitrification of a variety of ammonium sources such as atmospheric deposition, mineral and organic fertilizers and soil organic matter. A direct influence of mineral fertilizer, atmospheric deposition and sewage was excluded. Since temporal variation in stable isotopes of nitrate were detected only in surface water and locally at one groundwater monitoring well, aquifers appeared to be well mixed and influenced by a continuous nitrate input mainly from soil derived nitrogen. Hydrogeological analysis supported that the investigated aquifers were less vulnerable to rapid impacts due to long average transit times, ranging from 5 to 21 years. Our study revealed the importance of combining environmental tracer approaches and a comprehensive sampling campaign (local sources of nitrate, soil water, river water, and groundwater) to identify the nitrate sources in groundwater and its vulnerability. In future, the achieved results will help develop targeted strategies for a sustainable groundwater management focusing more on soil nitrogen storage.

For water samples from mining lake ML 111 of the Lusatian Lignite District and surrounding aquifers δ34S(SO4 −b), δ15N(NH4 +), δD, and δ18O (H2O) values have been determined to asess the flow dynamic of the in- and outflow scenario. The high mineralization and acidification (pH > 2.6) of the lake water results from an intensive interaction with the surrounding dump sites and the inflow of extremely sulfate rich dump water (up to 4,100mg/1 SO4 −). δ34S values range from −7‰ to + 7°CDT in the inflow aquifers. The lake water is considered to be a mixture of different water bodies. The evaporation signature in the outflow aquifer suggests that the groundwater consists of 60% lake water. The nitrogen transfer is explained by 15N signature of ammonium. Sulfate reduction, perceptible in outflow and dump aquifer, cannot be proved within the mining lake by 34S and hydrochemistry.

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.

This work aims to (1) identify the most conductive conditions for the generation of greenhouses gases (GHGs) in groundwater (e.g., hydrogeological contexts and geochemical processes) and (2) evaluate the indirect emissions of GHGs from groundwater at a regional scale in Wallonia (Belgium). To this end, nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations and the stable isotopes of nitrate (NO3-) and sulphate were monitored in 12 aquifers of the Walloon Region (Belgium). The concentrations of GHGs range from 0.05μg/L to 1631.2μg/L for N2O, 0μg/L to 17.1μg/L for CH4, and 1769 to 100,514ppm for the partial pressure of CO2 (pCO2). The highest average concentrations of N2O and pCO2 are found in a chalky aquifer. The coupled use of statistical techniques and stable isotopes is a useful approach to identify the geochemical conditions that control the occurrence of GHGs in the aquifers of the Walloon Region. The accumulation of N2O is most likely due to nitrification (high concentrations of dissolved oxygen and NO3- and null concentrations of ammonium) and, to a lesser extent, initial denitrification in a few sampling locations (medium concentrations of dissolved oxygen and NO3-). The oxic character found in groundwater is not prone to the accumulation of CH4 in Walloon aquifers. Nevertheless, groundwater is oversaturated with GHGs with respect to atmospheric equilibrium (especially for N2O and pCO2); the fluxes of N2O (0.32kgN2O-NHa-1y-1) and CO2 (27kgCO2Ha-1y-1) from groundwater are much lower than the direct emissions of N2O from agricultural soils and fossil-fuel-related CO2 emissions. Thus, indirect GHG emissions from the aquifers of the Walloon Region are likely to be a minor contributor to atmospheric GHG emissions, but their quantification would help to better constrain the nitrogen and carbon budgets.

The sustainable management of coastal marine environments requires a comprehensive understanding of the processes related to material transport from land to coastal sea. Besides surface water discharge (e.g., rivers and storm drains), submarine groundwater discharge (SGD) plays a key role since it provides a major pathway for solute and particulate transport of contaminants and nutrients, both having considerable potential to cause deterioration of the overall ecological status of coastal environments. The aim of the presented study was the investigation of SGD in two exemplary and dissimilar areas at the Black Sea coast, one in the west (Romania) and one in the east (Georgia). The approach included the assessment of the geological/geographical setting regarding the potential of SGD occurrence, the use of environmental tracer data (222Rn, δ18O, δ2H, salinity), and the evaluation of sea surface temperature patterns near the coastline using satellite data. Besides the individual site specific results, the study revealed that a combined evaluation of tracer data and satellite based information allows SGD localization with satisfying precision. A downscaling approach starting with large scale satellite data is generally recommended, continuing with medium scale tracer patterns and ending with local spot sampling.

Nitrate contamination in ground- and surface water is a persistent problem in countries with intense agriculture. The transition zone between rivers and their riparian aquifers, where river water and groundwater interact, may play an important role in mediating nitrate exports, as it can facilitate intensive denitrification, which permanently removes nitrate from the aquatic system. However, the in-situ factors controlling riparian denitrification are not fully understood, as they are often strongly linked and their effects superimpose each other. In this study, we present the evaluation of hydrochemical and isotopic data from a 2-year sampling period of river water and groundwater in the riparian zone along a 3rd order river in Central Germany. Based on bi- and multivariate statistics (Spearman's rank correlation and partial least squares regression) we can show, that highest rates for oxygen consumption and denitrification in the riparian aquifer occur where the fraction of infiltrated river water and at the same time groundwater temperature, are high. River discharge and depth to groundwater are additional explanatory variables for those reaction rates, but of minor importance. Our data and analyses suggest that at locations in the riparian aquifer, which show significant river water infiltration, heterotrophic microbial reactions in the riparian zone may be fueled by bioavailable organic carbon derived from the river water. We conclude that interactions between rivers and riparian groundwater are likely to be a key control of nitrate removal and should be considered as a measure to mitigate high nitrate exports from agricultural catchments.

Elevated nitrate concentrations are a thread for water supply and ecological integrity in surface water. Nitrate fluxes obtained by standard monitoring protocols at the catchment outlet strongly integrate spatially and temporally variable processes such as mobilization and turnover. Consequently, inference of dominant nitrate sources is often problematic and challenging in terms of effective river management and prioritization of measures. Here, we combine a spatially highly resolved assessment of nitrate concentration and fluxes along a mesoscale catchment with four years of monitoring data at two representative sites. The catchment is characterized by a strong land use gradient from pristine headwaters to lowland sub-catchments with intense agricultural land use and wastewater sources. We use nitrate concentrations in combination with hydrograph separation and isotopic fingerprinting methods to characterize and quantify nitrate source contribution. The hydrological analysis revealed a clear dominance of base flow during both campaigns. However, the absolute amounts of discharge differed considerably from one another (outlet: 1.42 m3 s− 1 in 2014, 0.43 m3 s− 1 in 2015). Nitrate concentrations are generally low in the pristine headwaters (

Due to the ability of stable water isotopes to characterize the origin of water and connected processes of groundwater recharge, we used the isotope variations of hydrogen and oxygen in different water sources for assessing the recharge process in the Dhofar region. δ(18)O and δ(2)H of precipitation, spring water, and groundwater cover a range from -10 to +2 and from -70 to +7 ‰ (vs Vienna Standard Mean Ocean Water), respectively, and correlate in a linear relationship close to the Global Meteoric Water Line. No obvious evaporation processes are detected. A clear signal of the recent precipitation is given by the annual monsoon. The monsoon signal is confirmed by several springs existing in the south at the foot of the Dhofar mountains and sources at Gogub above 450 m and Tawi Atir at 650 m above sea level. They occur here first in the form of water intercepted by trees as stemflow and throughflow. The isotope signature of groundwater in the Dhofar mountains reflects the climatic conditions at the time of recharge and the lithological features of the limestone matrix. To the north, the isotope patterns of the groundwater are continuously depleted from the monsoon signal along the outcropping aquifer D (Lower Umm Er Radhuma). Here, a more negative signature towards the wells in the Najd desert region was observed. Cyclone water that flooded wadis in the Dhofar region occasionally, as observed in November 2011, falls isotopically into the same range as we observed in the fossil groundwater. Taking into account the different sources of precipitation and groundwater and thus a clear distinction of the isotopic composition of the water sources, we conclude a recharge process divided into a southward and a northward component in the Dhofar region.

The groundwater in the Cambrian–Vendian aquifer system with its δ 18 O water values of about − 22‰ (VSMOW) and a low radiocarbon concentration is of glacial origin from the Last Ice Age. Earlier surveys have highlighted a negative co-variance of sulphate and bicarbonate content in the groundwater of the Cambrian–Vendian aquifer system, whereas the most depleted dissolved inorganic carbon δ 13 C values have been measured mainly in groundwater samples with the lowest sulphate concentrations. In this paper we studied the origin of sulphate and the factors controlling the sulphur and carbon isotope geochemistry in the aquifer system. Direct sources of sulphate were not found, but relying upon δ 18 O SO 4 measurements we suggest that the sulphate originates from oxidation of sulphide minerals whereas the δ 34 S of the dissolved SO 4 2 − in the groundwater is more enriched than the δ 34 S of the surrounding rocks. We show that bacterial activity may have caused the enrichment of δ 34 S of sulphate.

Oil sands tailings ponds in Alberta (Canada) are strongly stratified ecosystems structured in an upper water layer and underlying mud layers that harbour a diversity of microorganisms, contributing to hydrocarbon degradation and elemental cycling. Until now not much is known about the biogeochemistry of the ponds and their spatial structure is not well explored yet. An understanding of microbial activity and community composition is important, in particular, in order to determine potential effects on pond properties and long term development. Therefore, the purpose of the present study was to identify reactive zones of iron, carbon and sulfur cycling in an active tailings pond, by comparing biogeochemical data along two depth profiles. For both profiles a zone of intense sulfur cycling was substantiated by maxima of: (a) dissolved and solid sulfides; (b) sulfate reduction rates and thiosulfate oxidation potentials; and (c) viable counts of sulfate reducers and relative abundances of functional genes. In addition, methanogenesis and microbial iron reduction were shown to be important electron accepting processes in the ponds. All processes coexisted in a zone of intense elemental cycling at a depth of 1–4 m below the water–mud interface, where fresh tailings are likely to accumulate. Microbial activity and biomass decreased with depth, where tailings had higher age and density. While the upper mud layers were influenced by the presence of different archaea, the microbial communities showed an increased presence of bacterial species at depth. Insights from qPCR, 35 S radiotracer technique and stable isotope analysis mirrored some differences between the profiles, regarding sulfur and carbon cycling. Despite this, both profiles showed remarkably similar patterns of microbial community composition and activity, revealing a good reproducibility of biogeochemical cycling within a few metres.

The microbial oxidation of sulfide is a key reaction of the microbial sulfur cycle, recycling sulfur in its most reduced valence state back to more oxidized forms usable as electron acceptors. Under anoxic conditions, nitrate is a preferential electron acceptor for this process. Two enzymatic pathways have been proposed for sulfide oxidation under nitrate reducing conditions, the sulfide:quinone oxidoreductase (SQR) pathway and the Sox (sulfur oxidation) system. In experiments with the model strains Thiobacillus denitrificans and Sulfurimonas denitrificans, both pathways resulted in a similar small sulfur and oxygen isotope fractionation of -2.4 to -3.6‰ for (34)S and -2.4 to -3.4‰ for (18)O. A similar pattern was detected during the oxidation of sulfide in a column percolated with sulfidic, nitrate amended groundwater. In experiments with (18)O-labeled water, a strong oxygen isotope fractionation was observed for T. denitrificans and S. denitrificans, indicating a preferential incorporation of (18)O-depleted oxygen released as water by nitrate reduction to nitrogen. The study indicates that nitrate-dependent sulfide oxidation might be monitored in the environment by analysis of (18)O-depleted sulfate.

This article provides an overview about the Bode River catchment that was selected as the hydrological observatory and main region for hydro-ecological research within the TERrestrial ENvironmental Observatories Harz/Central German Lowland Observatory. It first provides information about the general characteristics of the catchment including climate, geology, soils, land use, water quality and aquatic ecology, followed by the description of the interdisciplinary research framework and the monitoring concept with the main components of the multi-scale and multi-temporal monitoring infrastructure. It also shows examples of interdisciplinary research projects aiming to advance the understanding of complex hydrological processes under natural and anthropogenic forcings and their interactions in a catchment context. The overview is complemented with research work conducted at a number of intensive research sites, each focusing on a particular functional zone or specific components and processes of the hydro-ecological system.

This contribution was preliminarily presented with an oral communication during the “Water Day 2015” conference organized in Rome the 20th of March 2015 by the Accademia Nazionale dei Lincei. It implements a recent paper that studied the Po river water from the Alpine springs toward the Adriatic Sea (Marchina et al. Environ Sci Pollut Res 22, 5184–5203, 2015), specifically focussing on its deltaic part. The new geochemical analyses are useful to evaluate the extent of salinization (due to mixing with sea-water) and to monitor the flux of nutrients that are conveyed by the river toward the coastal environment. The paper also contains oxygen/hydrogen water isotopes that represent a snapshot of the current climatic conditions to be compared with the literature data and with the future composition to set up a hydro-archive that should be updated to evaluate on-going climatic changes. Moreover, the paper reports preliminary nitrogen isotopes composition of Po river water that trace the impact of human activities, to be monitored in the future to understand possible on-going pollutions. We conclude that geochemical researches on Po river should consider with particular attention the delta because it is an extremely fragile ecosystem where biogeochemical variations are more relevant.