[1] Knowledge about the strength and travel times of hyporheic exchange is vital to predict reactive transport and biogeochemical cycling in streams. In this study, we outline how to perform and analyze stream tracer tests using pulse injections of fluorescein as conservative and resazurin as reactive tracer, which is selectively transformed to resorufin when exposed to metabolically active zones, presumably located in the hyporheic zone. We present steps of preliminary data analysis and apply a conceptually simple mathematical model of the tracer tests to separate effects of in-stream transport from hyporheic exchange processes. To overcome the dependence of common parameter estimation schemes on the initial guess, we derive posterior parameter probability density functions using an adaptive Markov chain Monte Carlo scheme. By this, we can identify maximum-likelihood parameter values of instream transport, strength of hyporheic exchange, distribution of hyporheic travel times as well as sorption and reactivity coefficients of the hyporheic zone. We demonstrate the approach by a tracer experiment at River Goldersbach in southern Germany (60 L/s discharge). In-stream breakthrough curves were recorded with online fluorometers and jointly fitted to simulations of a one-dimensional reactive transport model assuming an exponential hyporheic travel-time distribution. The findings show that the additional analysis of resazurin not only improved the physical basis of the modeling, but was crucial to differentiate between surface transport and hyporheic transient storage of stream solutes. Parameter uncertainties were usually small and could not explain parameter variability between adjacent monitoring stations. The latter as well as a systematic underestimation of the tailing are due to structural errors of the model, particularly the exponential hyporheic travel-time distribution. Mean hyporheic travel times were in the range of 12 min, suggesting that small streambed structures dominate hyporheic exchange at the study site.

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[1] Performing stream-tracer experiments is an accepted technique to assess transport characteristics of streams undergoing hyporheic exchange. Recently, combining conservative and reactive tracers, in which the latter presumably undergoes degradation exclusively within the hyporheic zone, has been suggested to study in-stream transport, hyporheic exchange, and the metabolic activity of the hyporheic zone. The combined quantitative analysis to adequately describe such tests, however, has been missing. In this paper, we present mathematical methods to jointly analyze breakthrough curves of a conservative tracer (fluorescein), a linearly degrading tracer (resazurin), and its daughter compound (resorufin), which are synchronously introduced into the stream as pulses. Instream transport is described by the one-dimensional advection-dispersion equation, amended with a convolution term to account for transient storage within the hyporheic zone over a distribution of travel times, transformation of the reactive tracer in the hyporheic zone, and two-site sorption of the parent and daughter compounds therein. We use a shapefree approach of describing the hyporheic travel-time distribution, overcoming the difficulty of identifying the best functional parameterization for transient storage. We discuss how this model can be fitted to the breakthrough curves of all three compounds and demonstrate the method by an application to a tracer test in the third-order stream Goldersbach in Southern Germany. The entire river water passes once through the hyporheic zone over a travel distance of about 200 m with mean hyporheic residence times ranging between 16 and 23 min. We also observed a secondary peak in the transfer functions at about 1 h indicating a second hyporheic flow path. We could jointly fit the breakthrough curves of all compounds in three monitoring stations and evaluated the parameter uncertainty of the individual and joint fits by a method based on conditional realizations of the hyporheic travel-time distribution. The approach gives insight into in-stream transport, hyporheic exchange, metabolic activity, and river-bed sorption of the stream under investigation.

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[1] Nitrate pollution from agricultural activities often persistently affects groundwater quality due to long residence times in the vadose and saturated zone. In this study we used a lumped parameter approach to estimate the residence time of groundwater and nitrate from the agriculturally used Jahna-Aue drinking water catchment in Saxonia, Germany. Inverse modeling of measured concentrations of tritium and tritiogenic 3 He revealed consistent mean residence times between 25 and 50 years for the young, nitrate-rich groundwater component, and high contributions (>75%) of an old, tracer-free, and nitratepoor groundwater. The obtained age distributions are in accordance with the complex hydrogeological situation of the investigated catchment, suggesting that the shallow and therefore most vulnerable part of the aquifer is not connected to the production wells. High residence times are supported by low concentrations of CFCs and by radiogenic 4 He as an independent age indicator. CFC concentrations only yield lower age limits due to identified problems with CFC contamination. Using the tracer-calibrated age distributions, future nitrate concentrations in the production wells most probably will remain below the drinking water limit because of the high dilution with old, nitrate-poor groundwater. Deterioration of the groundwater quality with respect to nitrate may occur if the groundwater pumping regime is changed so that the fraction of the younger, nitratebearing water is increased.

Many problems related to groundwater supply and quality, as well as groundwater-dependent ecosystems require some understanding of the timescales of flow and transport. For example, increased concern about the vulnerabilities of 'young' groundwaters (less than ~1000 years) to overexploitation, contamination, and land use/climate change effects are driving the need to understand flow and transport processes that occur over decadal, annual, or shorter timescales. Over the last few decades, a powerful suite of environmental tracers has emerged that can be used to interrogate a wide variety of young groundwater systems and provide information about groundwater ages/residence times appropriate to the timescales over which these systems respond. These tracer methods have distinct advantages over traditional approaches providing information about groundwater systems that would likely not be obtainable otherwise. The objective of this paper is to discuss how environmental tracers are used to characterise young groundwater systems so that more researchers, water managers, and policy-makers are aware of the value of environmental tracer approaches and can apply them in appropriate ways. We also discuss areas where additional research is required to improve ease of use and extend quantitative interpretations of tracer results.

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