Nitrate and Water Isotopes as Tools to Resolve Nitrate Travel Times in a Mixed Land Use Catchment

For the sake of food production, nutrients like nitrogen (N) are applied on agricultural land to supply crops. However, due to common agricultural practice, the amount of N provided very often significantly exceeds the uptake potential of the plants resulting in a N surplus that accumulates in the soil. Organic soil nitrogen is slowly transformed to nitrate, which is then mobilized by water and moves through the subsurface, with the risk of contaminating receiving water bodies. High nitrate loads cause poor chemical states for 27% of all groundwater bodies in Germany and foster eutrophication in lakes and rivers and by this a loss of biodiversity. The main problem are legacy issues of nitrate pollution, because there is a time lag between N input and nitrate mobilization and transport. Research on nitrate travel times is highly relevant for a reliable prediction of the capability of catchments to store, buffer and release nitrate. However, it is not clear how long nitrate is stored and transported in catchment’s storage. For this study, a 11 km2 headwater catchment with mixed land use within the Northern lowlands of the Harz mountains in Germany was investigated from spring 2017 until the end of 2020. A monitoring program was set up, starting with biweekly samples for the first two years and daily samples for the remainder, with sub-daily samples during precipitation events. Samples were taken from stream water and when available from precipitation water. Nitrate concentrations as well as isotopic signatures of water (δ18O and δ2H) and nitrate (δ18O and δ15N) were analysed. To investigate nitrate travel times, the numerical model tran-SAS (Benettin and Bertuzzo, 2018) was set up und modified for this catchment. Here, a time-variant power law function was used as rank StorAge Selection (SAS) function to select the composition of fluxes considering their age. Nitrate with a distinct δ18O from water, formed during microbial activities in the upper soil zone is transported with leaching water into the subsurface storage where denitrification with the corresponding isotope fractionation occurs. The combination of stable isotopes of water and biogeochemical equations to describe the forming of nitrate isotopes and the fractionation of nitrate isotopes during denitrification, which depends on transit times is a novel tool to investigate nitrate age and nitrate transport. Together with the usage of a SAS-based transit time model to simulate nitrate transport and denitrification in the subsurface, tran-SAS is transformed into a simplified reactive transport model (RTM). A decoupling between nitrate age and water age as well as between nitrate travel times and water travel times is expected. Especially during precipitation events catchment’s processes and travel times are changing due to altering hydrological conditions. The model allows to investigate the age of water and nitrate during different hydrological conditions. This will become more and more important considering more frequent hydrological extremes (droughts and floods) and associated N mobilization in agricultural catchments

Investigating River Water/Groundwater Interaction along a Rivulet Section by 222Rn Mass Balancing

Investigation of river water/groundwater interaction aims generally at: (i) localizing water migration pathways; and (ii) quantifying water and associated matter exchange between the two natural water resources. Related numerical models generally rely on model-specific parameters that represent the physical conditions of the catchment and suitable aqueous tracer data. A generally applicable approach for this purpose is based on the finite element model FINIFLUX that is using the radioactive noble gas radon-222 as naturally occurring tracer. During the study discussed in this paper, radon and physical stream data were used with the aim to localize and quantify groundwater discharge into a well-defined section of a small headwater stream. Besides site-specific results of two sampling campaigns, the outcomes of the study reveal: (i) the general difficulties of conducting river water/groundwater interaction studies in small and heterogeneous headwater catchments; and (ii) the particular challenge of defining well constrained site- and campaign-specific values for both the groundwater radon endmember and the radon degassing coefficient. It was revealed that determination of both parameters should be based on as many data sources as possible and include a critical assessment of the reasonability of the gathered and used datasets. The results of our study exposed potential limitations of the approach if executed in small and turbulent headwater streams. Hence, we want to emphasize that the project was not only executed as a case study at a distinct site but rather aimed at evaluating the applicability of the chosen approach for conducting river water/groundwater interaction studies in heterogeneous headwater catchments

New Ag3PO4 comparison material for stable oxygen isotope analysis

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 delta O-18 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 delta O-18 value was set to 0 parts per thousand and the normalization was done by a three-point linear regression using the reference materials IAEA-601, IAEA-602, and NBS127. Results The mean delta O-18 value of the new BOKU Ag3PO4 comparison material on the VSMOW-SLAP scale is 13.71 parts per thousand and the combined uncertainty is estimated as +/- 0.34 parts per thousand. 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.Peer reviewe

Investigating Groundwater Discharge into a Major River under Low Flow Conditions Based on a Radon Mass Balance Supported by Tritium Data

The potentially detrimental impact of groundwater discharge into rivers on the ecosystem services provided by the river makes the localization of groundwater discharge areas as well as the quantification of the associated mass fluxes an issue of major interest. However, localizing groundwater discharge zones and evaluating their impact are challenging tasks because of (i) the limited number of suitable tracers and (ii) the high spatio-temporal variability of groundwater/river water interaction in general. In this study, we applied the ubiquitous naturally occurring radioactive noble gas radon (222Rn) as an aqueous tracer to localize and quantify groundwater discharge along a 60 km reach of the upper German part of the major river Elbe under drought conditions. All radon data processing was executed with the numerical implicit finite element model FINIFLUX, a radon mass balance-based approach, which has been developed specifically to quantify the groundwater flux into rivers. The model results were compared to the tritium (3H) distribution pattern in the studied river reach. The results of the study proved the applicability of both (i) the methodical approach (i.e., radon as tracer) and (ii) the application of FINIFLUX to drought conditions (with river discharge rates as low as 82 m3/s vs. a long time mean of 300 m3/s). Applying the model, the recorded dataset allowed differentiating between groundwater baseflow, on the one hand, and interflow and surface water runoff distributions to the river, on the other. Furthermore, the model results allowed assessing the location and the intensity of groundwater discharge into the river under low flow conditions. It was also shown that analysing discrete river water samples taken from distinct points in a major stream might lead to slightly incorrect results because of an incomplete mixing of river water and locally discharging groundwater. An integrating sampling approach (as applied for radon) is preferable here

Natural and anthropogenic variations in the Po river waters (northern Italy): insights from a multi-isotope approach

Po is the main Italian river and the δ18O and δ2H of its water reveal a similarity between the current meteoric fingerprint and that of the past represented by groundwater. As concerns the hydrochemisty, the Ca–HCO3 facies remained constant over the last 50 year, and only nitrate significantly increased from less than 1 mg/L to more than 10 mg/L in the 1980s, and then attenuated to a value of 9 mg/L. Coherently, δ13C and δ34S are compatible with the weathering of the lithologies outcropping in the basin, while extremely variable δ15NNO3 indicates contribution from pollutants released by urban, agricultural and zootechnical activities. This suggests that although the origin of the main constituents of the Po river water is geogenic, anthropogenic contributions are locally significant. Noteworthy, the associated aquifers have the same nitrogen isotopic signature of the Po river, but are characterized by significantly higher NO3 concentration. This implies that aquifers’ pollution is not ascribed to inflow of current river water, and that the attenuation of the nitrogen load recorded in the river is not occurring in the aquifers, due to their longer water residence time and delayed recovery from anthropogenic contamination

Submarine Groundwater Discharge at a Single Spot Location: Evaluation of Different Detection Approaches

Submarine groundwater discharge (SGD) into the ocean is of general interest because it acts as vehicle for the transport of dissolved contaminants and/or nutrients into the coastal sea and because it may be accompanied by the loss of significant volumes of freshwater. Due to the large-scale and long-term nature of the related hydrological processes, environmental tracers are required for SGD investigation. The water parameters of electrical conductivity and temperature, the naturally occurring radionuclides of radon and radium as well as the stable water isotopes 18O and 2H have proven in previous studies their general suitability for the detection and quantification of SGD. However, individual hydrogeological settings require a site-specific application of this “tool box”. This study evaluates and compares the applicability of the abovementioned tracers for investigating SGD from a distinct submarine source in a karst environment at Cabbé, southern France. The specific advantages and disadvantages of each individual parameter under the given hydrogeological conditions are discussed. Radon appeared to be the most suitable environmental tracer in the site specific context. The water temperature was less reliable due to the little temperature difference between seawater and groundwater and since the diurnal variation of the air temperature masks potential SGD signals. Radium isotopes are less applicable in the studied region due to the lack of a well-developed subterranean estuary. The stable water isotopes showed results consistent with the salinity and radon data; however, the significantly higher effort required for stable isotope analyses is disadvantageous. A multi-temporal thermal remote sensing approach proved to be a powerful tool for initial SGD surveying

A hydrochemical - isotopic approach for assessing factors controlling the regional pollution of an urban aquifer

The alluvial aquifer of the Meuse River is contaminated at regional scale in the urbanized and industrialized area of Liège in Belgium, in particular inorganics pollutants such as sulfate, nitrate and ammonium. The sources of those contaminants are numerous: brownfields, urban waste water, subsurface acid mine drainage from former coal mines, atmospheric deposits related to former pollutants emissions in the atmosphere ... Sulfate, nitrate and ammonium are both typical pollutants of the aquifer and tracers of the possible pollution sources. In the Water Framework Directive context, a detailed hydrogeochemical characterization of groundwater was performed. The aim is to determine the origin of the inorganic contaminations, the main processes contributing to poor groundwater quality and the spatial extent of the contaminations. A large hydrochemical sampling campaign was performed, based on 71 selected representative sampling locations, to better characterize the different vectors (end-members) of contamination of the alluvial aquifer and their respective contribution to groundwater contamination in the area. Groundwater samples were collected and analyzed for major and minor compounds and metallic trace elements. The analyses also include stable isotopes in water, sulfate, nitrate, ammonium, dissolved inorganic carbon, boron and strontium. Different hydrogeochemical approaches are combined to obtain a global understanding of the hydrogeochemical processes at regional scale. Hydrochemical interpretations are based on classical diagrams, spatial distribution maps, geochemical equations, multivariate statistics such as self-organizing maps and isotopic analyses. With this combined approach, the location of the contaminant sources and most contaminated sectors of the alluvial aquifer together with a better understanding of geochemical processes involved are obtained. Redox processes strongly influence the composition of groundwater, specifically for compounds degrading the quality of groundwater in the area (sulfate, nitrate and ammonium). The highest concentrations of sulfate can be associated with the post-mining stage in the acid mine drainage process. Various reactions involving nitrogen compounds have been identified and allow a better understanding of causes of high concentrations of ammonium and nitrate. Denitrification and sulphate reduction are also demonstrated based on isotopic ratios

Age and origin of groundwater resources in the Ararat Valley, Armenia: a baseline study applying hydrogeochemistry and environmental tracers

Within the Ararat Valley (Armenia), a continuously growing water demand (for irrigation and fish farming) and a simultaneous decline in groundwater recharge (due to climate change) result in increasing stress on the local groundwater resources. This detrimental development is reflected by groundwater-level drops and an associated reduction of the area with artesian conditions in the valley centre. This situation calls for increasing efforts aimed at more sustainable water resources management. The aim of this baseline study was the collection of data that allows for study on the origin and age distribution of the Ararat Valley groundwater based on environmental tracers, namely stable (δ2H, δ18O) and radioactive (35S, 3H) isotopes, as well as physical-chemical indicators. The results show that the Ararat Valley receives modern recharge, despite its (semi-)arid climate. While subannual groundwater residence times could be disproved (35S), the detected 3H pattern suggests groundwater ages of several decades, with the oldest waters being recharged around 60 years ago. The differing groundwater ages are reflected by varying scatter of stable isotope and hydrochemical signatures. The presence of young groundwater (i.e., younger that the 1970s), some containing nitrate, indicates groundwater vulnerability and underscores the importance of increased efforts to achieve sustainable management of this natural resource. Since stable isotope signatures indicate the recharge areas to be located in the mountains surrounding the valley, these efforts must not be limited to the central part of the valley where most of the abstraction wells are located.Technische Universität Darmstadt (3139

Occurrence of greenhouse gases in the aquifers of the Walloon Region (Belgium)

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 0.05 µg/L to 1631.2 µg/L for N2O, 0 µg/L to 17.1 µg/L for CH4, and 1769 to 100,514 ppm 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 (0.32 kg N2O-N Ha-1 y-1) and CO2 (27 kg CO2 Ha-1 y-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