Stable water isotopes and tritium tracers tell the same tale: no evidence for underestimation of catchment transit times inferred by stable isotopes in StorAge Selection (SAS)-function models

Stable isotopes (δ18O) and tritium (3H) are frequently used as tracers in environmental sciences to estimate age distributions of water. However, it has previously been argued that seasonally variable tracers, such as δ18O, generally and systematically fail to detect the tails of water age distributions and therefore substantially underestimate water ages as compared to radioactive tracers such as 3H. In this study for the Neckar River basin in central Europe and based on a &gt;20-year record of hydrological, δ18O and 3H data, we systematically scrutinized the above postulate together with the potential role of spatial aggregation effects in exacerbating the underestimation of water ages. This was done by comparing water age distributions inferred from δ18O and 3H with a total of 21 different model implementations, including time-invariant, lumped-parameter sine-wave (SW) and convolution integral (CO) models as well as StorAge Selection (SAS)-function models (P-SAS) and integrated hydrological models in combination with SAS functions (IM-SAS). We found that, indeed, water ages inferred from δ18O with commonly used SW and CO models are with mean transit times (MTTs) of ∼ 1–2 years substantially lower than those obtained from 3H with the same models, reaching MTTs of ∼10 years. In contrast, several implementations of P-SAS and IM-SAS models not only allowed simultaneous representations of storage variations and streamflow as well as δ18O and 3H stream signals, but water ages inferred from δ18O with these models were, with MTTs of ∼ 11–17 years, also much higher and similar to those inferred from 3H, which suggested MTTs of ∼ 11–13 years. Characterized by similar parameter posterior distributions, in particular for parameters that control water age, P-SAS and IM-SAS model implementations individually constrained with δ18O or 3H observations exhibited only limited differences in the magnitudes of water ages in different parts of the models and in the temporal variability of transit time distributions (TTDs) in response to changing wetness conditions. This suggests that both tracers lead to comparable descriptions of how water is routed through the system. These findings provide evidence that allowed us to reject the hypothesis that δ18O as a tracer generally and systematically “cannot see water older than about 4 years” and that it truncates the corresponding tails in water age distributions, leading to underestimations of water ages. Instead, our results provide evidence for a broad equivalence of δ18O and 3H as age tracers for systems characterized by MTTs of at least 15–20 years. The question to which degree aggregation of spatial heterogeneity can further adversely affect estimates of water ages remains unresolved as the lumped and distributed implementations of the IM-SAS model provided inconclusive results. Overall, this study demonstrates that previously reported underestimations of water ages are most likely not a result of the use of δ18O or other seasonally variable tracers per se. Rather, these underestimations can largely be attributed to choices of model approaches and complexity not considering transient hydrological conditions next to tracer aspects. Given the additional vulnerability of time-invariant, lumped SW and CO model approaches in combination with δ18O to substantially underestimate water ages due to spatial aggregation and potentially other still unknown effects, we therefore advocate avoiding the use of this model type in combination with seasonally variable tracers if possible and instead adopting SAS-based models or time-variant formulations of CO models.</p

Effect of particle density on microplastics transport in artificial and natural porous media

The occurrence and persistence of microplastics (MPs) in natural environments are of increasing concern. Along with this, the transport of MPs in sediments has been investigated mainly focusing on the effect of plastic size and shape, media size effect, and solution chemistry. Yet, the influence of particle density is only partially understood. Therefore, column experiments on the transport of variably buoyant MPs in saturated natural sediments and glass beads were conducted, and transport parameters were quantified using a two-site kinetic transport model with a depth-dependent blocking function (the amount of retained MPs does not decrease at a constant rate with increasing depth, the majority of MPs were retained near the column inlet). Neutral, sinking, and buoyant MPs within the same size range were selected, with stable water isotope applied as conservative tracer to explore water and MP movement in the tested sediments. The results showed that 95.5 ± 1.4% of sinking MPs remained in columns packed with gravel, followed by buoyant and neutral MPs, thus indicating that particle density does affect MP mobility. Similar recovered amounts of MPs were found in columns packed with glass beads, indicating that tested sediment types do not affect the deposition behavior of MPs. The breakthrough curves of MPs were accurately described by the selected model. However, the simulated retention profiles overestimated the observed MP amount in layers closest to the column inlet. The coupled experimental and modeled results suggest an enhanced retention of sinking MPs, while neutrally and buoyant MPs exhibit a higher mobility in comparison. Thus, neutral or buoyant MPs can potentially pose a higher contamination risk to subsurface porous media environments compared to sinking MPs. Discrepancies between observed and simulated retention profiles indicate that future model development is needed for advancing the MP deposition as affected by particle density

Experimental and simulated microplastics transport in saturated natural sediments: impact of grain size and particle size

Microplastics (MPs) present in terrestrial environments show potential leaching risk to deeper soil layers and aquifer systems, which threaten soil health and drinking water supply. However, little is known about the environmental fate of MPs in natural sediments. To examine the MPs transport mechanisms in natural sediments, column experiments were conducted using different natural sediments and MPs (10–150 µm) with conservative tracer. Particle breakthrough curves (BTCs) and retention profiles (RPs) were numerically interpreted in HYDRUS-1D using three different models to identify the most plausible deposition mechanism of MPs. Results show that the retention efficiency for a given particle size increased with decreasing grain size, and RPs exacerbated their hyper-exponential shape in finer sediments. Furthermore, the amounts of MPs present in the effluent increased to over 85 % as MPs size decreased to 10–20 µm in both gravel and coarse sand columns, while all larger MPs (125–150 µm) were retained in the coarse sand column. The modeling results suggested that the blocking mechanism becomes more important with increasing particle sizes. In particular, the attachment-detachment without blocking was the most suited parameterization to interpret the movement of small MPs, while a depth-dependent blocking approach was necessary to adequately describe the fate of larger particles

Constraining a flow model with field measurements to assess water transit time through a vadose zone

The modeling of thick vadose zones is particularly challenging because of difficulties in collecting a variety of measured sediment properties, which are required for parameterizing the model. Some models rely on synthetic data, whereas others are simplified by running as homogeneous sediment domains and relying on a single set of sediment properties. Few studies have simulated flow processes through a thick vadose zone using real and comprehensive data sets comprising multiple measurements. Here, we develop a flow model for a 7‐m‐thick vadose zone. This model, combining the numerical codes CTRAN/W with SEEP/W, includes the measured sediment hydraulic properties of the investigated vadose zone and incorporates the actual climate and subsurface conditions of the study site (precipitations, water‐table elevations, and stable isotope data). The model is calibrated by fitting the simulated and measured vertical profiles of water content. Our flow model calculates a transit time of 1 year for the travel of water through the 7‐m vadose zone; this estimate matches stable isotope‐based results obtained previously for this site. A homogeneous sediment domain flow model, which considers only a single set of sediment properties, produces a transit time that is approximately half the duration of that of the heterogeneous flow model. This difference highlights the importance of assuming heterogeneous material within models of thick vadose zones and testifies to the advantage gained when using real sediment hydraulic properties to parametrize a flow model

Assessing groundwater recharge and transpiration in a humid northern region dominated by snowmelt using vadose-zone depth profiles

Profiles of the stable isotope ratios of pore water within the vadose zone provide fingerprints of the history of water percolation into a soil. These profiles, combined with profiles of the volumetric water content, can determine the timing and amount of water that has percolated during specific periods. This study aims to: (1) understand water percolation at two sites in Quebec (Canada) that experience thick snow coverage during the winter season; (2) calculate groundwater recharge rates using the peak-shift method; and (3) estimate the transpiration rate based on the water balance budget. A 7-m-deep borehole was drilled at two sites: one site is sparsely covered by vegetation (S1), while the second underlies a pine forest (S2). For all subsamples, δ18O and δ2H from the soil pore water were analyzed, volumetric water content of the cores was measured, and grain-size analyses to estimate the hydraulic properties were performed. For both boreholes, the winter–spring and summer–autumn periods were determined. Given the limited evapotranspiration occurring during the winter–spring period, recharge rates were high at both sites (71 and 75%), while the summer–autumn period had lower recharge rates of 63% (S1) and 41% (S2). A transpiration rate of 0.7 mm/day was estimated for the pine trees covering site S2. This study provides new field observations for estimating recharge based on water stable isotope profiles in a humid northern region dominated by snowmelt. Moreover, it confirms the accuracy of the peak-shift method for assessing groundwater recharge and estimating transpiration. Les profils du taux d’isotopes stables de l’eau des pores de la zone vadose fournissent des empreintes de l’histoire de la percolation de l’eau dans le sol. Ces profils, combinés à des profils de teneurs volumétriques en eau, peuvent déterminer le moment et la quantité d’eau qui a percolé pendant des périodes particulières. Cette étude a pour objectifs: (1) de comprendre la percolation de l’eau sur deux sites du Québec (Canada) qui connaissent un épais manteau neigeux pendant l’hiver; (2) de calculer les taux de recharge en appliquant la méthode du « décalage du pic »; (3) d’estimer le taux de transpiration sur la base du bilan hydrologique. Un forage de 7 m de profondeur a été réalisé sur les deux sites: le premier site est couvert d’une végétation clairsemée (S1), tandis que le deuxième se situe sous une forêt de pins (S2). Pour tous les échantillons, le δ18O et le δ2H de l’eau des pores du sol ont été analysés, la teneur volumétrique en eau des carottes mesurée et des analyses de la granulométrie conduites afin d’estimer les propriétés hydrauliques. Pour les deux forages, les périodes hiver–printemps et été–automne ont été définies. Etant donnée la faible évapotranspiration durant la période hiver–printemps, les taux de recharge sont élevés sur les deux sites (71 et 75%), tandis que la période été–automne montre des taux de recharge plus faibles, de 63% (S1) et 41% (S2). Un taux de transpiration de 0,7 mm/jour a été estimé pour la forêt de pins couvrant le site S2. Cette étude fournit des observations de terrain inédites pour estimer, sur la base de profils d’isotopes stables de l’eau, la recharge d’une région nordique humide dominée par la fonte des neiges. De plus, elle confirme la précision de la méthode du « décalage du pic » pour évaluer la recharge et estimer la transpiration

Inverted phenology of Faidherbia albida paced with the dynamics of the water table

Faidherbia albida is an emblematic species of agro-sylvo-pastoralism in African semi-arid areas. It combines inverted phenology (strong growth, N-fixation and production of highly palatable fodder during the dry season, ideal for livestock), defoliation during the rainy season (ideal for minimizing competition with crops) and use of deep resources mainly (riparian in its natural habitat, phreatophyte in parklands, deeply rooted, avoiding drought stress, using mostly groundwater (isotopic evidence), ideal for recycling). What could drive the inverted phenology then? Past research most often sought to correlate its peculiar phenology with climate variables, but hardly considered its deep roots and phreatophyte behavior. We set up a collaborative observatory (Faidherbia-Flux ) in a Senegal parkland in 2018 and monitored the foliar phenology of 15 adult trees (LAI2000), radial growth, sap flow and wood water content (capacitive probes). We also monitored the dynamics of soil humidity (TDR profiles) and water table fluctuations (5-6 m, piezometers). Drainage did reach the water table, but its maximum level was delayed till the end of the wet season, corresponding to the time when Faidherbia emitted new leaves. 100% foliage was maintained until the end of December, concurrently with a maximum growth, sap flow and water table level. From January to July (driest period), we observed a slow decrease in the water table level, foliage and transpiration, all reaching minima by the end of July (start of the defoliated phase), but no drought stress. Interestingly, wood rehydrated till end of the rainy season (September-October). Considering such coincidences between deep hydrological (delayed rewatering), wood rehydratation and phenological phases (inverted phenology), we suggest that this deeply rooted and phreatophyte species adjusts its phenology according to the water table and wood water content, shedding leaves when those levels reached minimum and bursting only when they resumed to maximum

Differentiated spring behavior under changing hydrological conditions in an alpine karst aquifer

Limestone massifs with a high density of dolines form important karst aquifers in most of the Alps, often with groundwater circulating through deep karst conduits and water coming out of closely spaced springs with flow rates of over some cubic meters per second. Although several hydrogeological studies and tracing experiments were carried out in many of these carbonate mountains in the past, the hydrogeology of most of these karst aquifers is still poorly known. Geological, hydrodynamic and hydrochemical investigations have been carried out in one of the most representative of these areas (Cansiglio-Monte Cavallo, NE Italy) since spring 2015, in order to enhance the knowledge on this important type of aquifer system. Additionally, a cave-to-spring multitracer test was carried out in late spring 2016 by using three different fluorescent tracers. This hydrogeological study allowed: 1) gathering new detailed information on the geological and tectonic structure of such alpine karst plateau; 2) defining discharge rates of the three main springs (Gorgazzo, Santissima, and Molinetto) by constructing rating curves; 3) understanding the discharging behavior of the system with respect to different recharge conditions; 4) better defining the recharge areas of the three springs. The three nearby springs (the spring front stretches over 5 km), that drain the investigated karst aquifer system, show different behaviors with respect to changing discharge conditions, demonstrating this aquifer to be divided in partially independent drainage systems under low-flow conditions, when their chemistry is clearly differentiated. Under high-flow conditions, waters discharging at all springs show more similar geochemical characteristics. The combination of geochemistry, hydrodynamic monitoring and dye tracing tests has shown that the three springs have different recharge areas. The study points out that even closely spaced karst springs, that apparently drain the same karst mountain, can have different behaviors, and thus distinctive reactions toward polluting events, a characteristic to be taken into account for their management

Differentiated karst spring behavior under changing hydrological conditions in the Cansiglio-Cavallo area (italian Alps)

Veneto, Friuli-Venezia Giulia, karst aquifer, water budget

Comparison of two isotopic hydrograph separation methods in the Hydrological Open Air Laboratory, Austria

Exploring the contributions of new and old water to runoff during precipitation events in agricultural catchments is essential for understanding runoff generation, solute transport, and soil erosion. The aim of this study was to investigate the variability in the isotopic composition of precipitation and runoff in the 66 ha agricultural catchment in Austria, in the Hydrological Open Air Laboratory (HOAL), in order to compare two isotope hydrograph separation methods. The classical two-component (IHS) and the ensemble hydrograph separation (EHS) were applied to multiple large events in May–October of 2013–2018 using δ18O and δ2H. The peak flow new water contributions obtained by IHS were compared with the average new water fraction from EHS. The average new water fraction calculated with EHS based on regular weekly sampling was close to zero, which can be explained by the large diffuse groundwater discharge into the stream between the events. When only investigating events with high temporal resolution sampling, the results suggest that EHS provided average new water fractions during peak flows (0.46 ± 0.04 for δ18O, 0.47 ± 0.03 for δ2H) that were close to the averages obtained by IHS (0.47 for δ18O, 0.50 for δ2H). New water fractions tended to be higher for larger rainfall intensities. High peak flow new water fractions could be explained by the agricultural land use and soils with low permeability promoting overland flow generation and by some of the tile drainage systems contributing to the delivery of water. In conclusion, a weekly sampling frequency was not sufficient in the HOAL but instead high-resolution sampling during events was necessary to estimate the average new water contributions during events. While EHS may be a more robust approach compared to IHS, as it relaxes some of the assumptions of IHS, IHS can provide information on the variability of new water contributions of individual events

Dynamics of pathogens and fecal indicators during riverbank filtration in times of high and low river levels

Riverbank filtration is an established and quantitatively important approach to mine high-quality raw water for drinking water production. Bacterial fecal indicators are routinely used to monitor hygienic raw water quality, however, their applicability in viral contamination has been questioned repeatedly. Additionally, there are concerns that the increasing frequency and intensity of meteorological and hydrological events, i.e., heavy precipitation and droughts leading to high and low river levels, may impair riverbank filtration performance. In this study, we explored the removal of adenovirus compared with several commonly used bacterial and viral water quality indicators during different river levels. In a seasonal study, water from the Rhine River, a series of groundwater monitoring wells, and a production well were regularly collected and analyzed for adenovirus, coliphages, E. coli, C. perfringens, coliform bacteria, the total number of prokaryotic cells (TCC), and the number of virus-like particles (TVPC) using molecular and cultivation-based assays. Additionally, basic physico-chemical parameters, including temperature, pH, dissolved organic carbon, and nutrients, were measured. The highest log10 reduction during the >72 m of riverbank filtration from the river channel to the production well was observed for coliforms (>3.7 log10), followed by E. coli (>3.4 log10), somatic coliphages (>3.1 log10), C. perfringens (>2.5 log10), and F+ coliphages (>2.1 log10) at high river levels. Adenovirus decreased by 1.6–3.1 log units in the first monitoring well (>32 m) and was not detected in further distant wells. The highest removal efficiency of adenovirus and most other viral and bacterial fecal indicators was achieved during high river levels, which were characterized by increased numbers of pathogens and indicators. During low river levels, coliforms and C. perfringens were occasionally present in raw water at the production well. Adenovirus, quantified via droplet digital PCR, correlated with E. coli, somatic coliphages, TCC, TVPC, pH, and DOC at high river levels. At low river levels, adenoviruses correlated with coliforms, TVPC, pH, and water travel time. We conclude that although standard fecal indicators are insufficient for assessing hygienic raw water quality, a combination of E. coli, coliforms and somatic coliphages can assess riverbank filtration performance in adenovirus removal. Furthermore, effects of extreme hydrological events should be studied on an event-to-event basis at high spatial and temporal resolutions. Finally, there is an urgent need for a lower limit of detection for pathogenic viruses in natural waters. Preconcentration of viral particles from larger water volumes (>100 L) constitutes a promising strategy