Transit time distributions (TTDs) are crucial descriptors of flow and transport processes in catchments, which can be determined from stable water isotope data. Recently, the young water fraction (F yw ) has been introduced as an additional metric derivable from seasonal isotope cycles. In this study, we calculated F yw and TTDs using monthly isotope data from 24 contrasting subcatchments in a mesoscale catchment (3,300 km 2 ) in Germany. F yw ranged from 0.01 to 0.27 (mean = 0.11) and was smallest in mountainous catchments. Assuming gamma-shaped TTDs, we determined stationary TTDs with the convolution integral method for each subcatchment. The convolution integral was first calibrated against the isotope data only (i.e., traditional calibration) and, second, using a multiobjective calibration with the F yw estimates as an additional constraint. This yielded largely differing TTD parameters even for neighboring catchments, with F yw values below 0.1 generally involving a delayed peak in TTDs (i.e., gamma-distribution shape parameter > 1). While the traditional calibration resulted in large uncertainties in TTD parameters, these uncertainties were reduced with the multiobjective calibration, thereby improving the assessment of mean transit times (2 years on average, ranging between 9.6 months and 5.6 years). This highlights the need for uncertainty assessment when using simple isotope models and shows that the traditional calibration might not yield an optimum solution in that it may give a TTD nonconsistent with F yw . Given the robustness of F yw estimates, isotope models should thus aim at accurately describing both F yw and measured isotope data in order to improve the description of flow and transport in catchments.Plain Language Summary Information on the age of river water is crucial for assessing the vulnerability of rivers to weather extremes and pollution. The age of river water is defined as the time that water has spent underground after rainfall infiltration and before ending up in the river. The probability distribution of river water age can be determined using environmental tracers, which are tracers that naturally occur in the system such as stable water isotopes. In this study, we used isotope models to analyze time series of stable water isotopes in rainfall and streamwater measured in 24 subcatchments of the Bode catchment in central Germany. We found that the mean age of river water ranges between 9.6 months and 5.6 years depending on catchment characteristics such as climate and soil type. Moreover, river water with an age of below 2 to 3 months accounts for between 1% and 27% of the entire age distribution. We demonstrate how to use this information on young river water to constrain other metrics such as the mean water age. We suggest that this method is valuable for future studies using environmental tracers and models to determine water age in catchments.

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ScaleX is a collaborative measurement campaign, collocated with a long-term environmental observatory of the German Terrestrial Environmental Observatories (TERENO) network in the mountainous terrain of the Bavarian Prealps, Germany. The aims of both TERENO and ScaleX include the measurement and modeling of land surface–atmosphere interactions of energy, water, and greenhouse gases. ScaleX is motivated by the recognition that long-term intensive observational research over years or decades must be based on well-proven, mostly automated measurement systems, concentrated in a small number of locations. In contrast, short-term intensive campaigns offer the opportunity to assess spatial distributions and gradients by concentrated instrument deployments, and by mobile sensors (ground and/or airborne) to obtain transects and three-dimensional patterns of atmospheric, surface, or soil variables and processes. Moreover, intensive campaigns are ideal proving grounds for innovative instruments, methods, and techniques to measure quantities that cannot (yet) be automated or deployed over long time periods. ScaleX is distinctive in its design, which combines the benefits of a long-term environmental-monitoring approach (TERENO) with the versatility and innovative power of a series of intensive campaigns, to bridge across a wide span of spatial and temporal scales. This contribution presents the concept and first data products of ScaleX-2015, which occurred in June–July 2015. The second installment of ScaleX took place in summer 2016 and periodic further ScaleX campaigns are planned throughout the lifetime of TERENO. This paper calls for collaboration in future ScaleX campaigns or to use our data in modelling studies. It is also an invitation to emulate the ScaleX concept at other long-term observatories.

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.

Interactions between hydrological characteristics and microbial activities affect the isotopic composition of dissolved nitrate in surface water. Nitrogen and oxygen isotopic signatures of riverine nitrate in 133 sampling locations distributed over the Bode River catchment in the Harz Mountains, Germany, were used to identify nitrate sources and transformation processes. An annual monitoring programme consisting of seasonal sampling campaigns in spring, summer and autumn was conducted. δ(15)N and δ(18)O of nitrate and corresponding concentrations were measured as well as δ(2)H and δ(18)O of water to determine the deuterium excess. In addition, precipitation on 25 sampling stations was sampled and considered as a potential input factor. The Bode River catchment is strongly influenced by agricultural land use which is about 70 % of the overall size of the catchment. Different nitrogen sources such as ammonia (NH4) fertilizer, soil nitrogen, organic fertilizer or nitrate in precipitation show partly clear nitrate isotopic differences. Processes such as microbial denitrification result in fractionation and lead to an increase in δ(15)N of nitrate. We observed an evident regional and partly temporal variation of nitrate isotope signatures which are clearly different between main landscape types. Spring water sections within the high mountains contain nitrate in low concentrations with low δ(15)NNO3 values of -3 ‰ and high δ(18)ONO3 values up to 13 ‰. High mountain stream water sub-catchments dominated by nearly undisturbed forest and grassland contribute nitrate with δ(15)NNO3 and δ(18)ONO3 values of -1 and -3.5 ‰, respectively. In the further flow path, which is affected by an increasing agricultural land use and urban sewage, we recognized an increase in δ(15)NNO3 and δ(18)ONO3 up to 22 and 18 ‰, respectively, with high variations during the year. A correlation seems to exist between the percentage of agricultural land use area and the corresponding δ(15)NNO3 values for sub-catchments. A shift towards heavier isotope values in stream water samples taken in July 2012 is significant (p-value = 6 · 10(-6)) compared to samples from March and October 2012. We also see a season-depending impact of microbial denitrification. Denitrification, especially evident in the lowlands, predominantly takes place in the riverbeds. In addition, mixing processes of different nitrate sources and temperature-depending biological processes such as nitrification have to be taken into consideration. Constant-tempered groundwater does not play a noticeable role in the processes of the stream water system. As constrained from oxygen isotope signatures, precipitation associated with low nitrate concentrations does not have an obvious impact on stream water nitrate in the high mountain region.

Although aquifers are naturally heterogeneous, the interpretation of pumping tests is commonly performed under the assumption of aquifer homogeneity. This yields interpreted hydraulic parameters averaged over a domain of uncertain extent which disguises their relation to the underlying heterogeneity. In this study, we numerically investigate the sensitivity of the transient drawdown at the pumping well, to nonuniform distributions of transmissivity in confined aquifers. Frechet kernels and their time derivative are used to estimate two spatially averaged transmissivities, denoted the equivalent and interpreted transmissivity, T eq and T in , respectively, for the case of single-well pumping tests. Interrelating T eq and T in is achieved by modeling T in in terms of a distance dependent, radially heterogeneous field. In weakly heterogeneous aquifers, T eq approximates T PW , the local transmissivity at the pumped well. With increasing degree of heterogeneity, T eq deviates from T PW as pumping propagates. T in starts at T PW , approaching the spatial geometric mean of transmissivity during late pumping times. Limits of the proposed spatial weighting functions are investigated by treating the interpreted storativity, S est , as an indicator for flow connectivity. It is shown numerically that the spatial weights for T eq and T in agree well to the underlying heterogeneity if S est < 1. Finally, implications for applying the concepts of T eq and T in to heterogeneous domains, and, for real world applications are discussed. It is found that time-dependent spatial averages of T in agree well with estimates of the interpreted transmissivity from the Continuous-Derivation method.

Urban areas are the focus of major ecological, social and economical activity. They are thus also prime locations of increasing conflict with regard to water use and water protection. As a direct and/or indirect consequence of urban land use and human activity, urban water systems are frequently polluted with organic contaminants including waste water-born xenobiotics such as pharmaceuticals, personal care products (collectively known as PPCPs) and endocrine-active substances. This study reviews new integrated methodologies including flux calculations as well as chemical investigations for determining the impact of human activities on urban water systems and on processes within the urban watershed. The use of indicator substances, representing different contaminant sources and pathways, integral pumping tests and mass balance approaches are suitable alternatives within these environments. The issues are explored using contaminant mass balance examples from Halle/Saale and Leipzig, Germany.

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