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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.

Nitrate reduction constitutes an important natural mechanism to mitigate the widespread and persistent nitrate contamination of groundwater resources. In fractured aquifers, however, the abundance and accessibility of electron donors and their spatial correlation with groundwater flow paths are often poorly understood. In this study, the nitrate reduction potential of a fractured carbonate aquifer in the Upper Muschelkalk of SW Germany was investigated, where denitrification is due to the oxidation of ferrous iron and reduced sulfur. Petrographical analyses of rock samples revealed concentrations of syn-sedimentary and diagenetically formed pyrite ranging from 1 to 4 wt.% with only small differences between different facies types. Additional ferrous iron is available in saddle dolomites (up to 2.6 wt.%), which probably were formed by tectonically induced percolation of low-temperature hydrothermal fluids. Borehole logging at groundwater wells (flowmeter, video, gamma) indicates that most groundwater flow occurs along karstified bedding planes partly located within dolomites of the shoal and backshoal facies. The high porosity (15–30%) of these facies facilitates molecular diffusive exchange of solutes between flow paths in the fractures and the reactive minerals in the pore matrix. The high-porosity facies together with hydraulically active fractures featuring pyrite or saddle dolomite precipitates constitute the zones of highest nitrate reduction potential within the aquifer. Model-based estimates of electron acceptor/donor balances indicate that the nitrate reduction potential protecting water supply wells increases with increasing porosity of the rock matrix and decreases with increasing hydraulic conductivity (or effective fracture aperture) and spacing of the fracture network.

Floodplains are often conceptualized as homogeneous sediment bodies which connect streams with their respective catchment and buffer agricultural inputs. This has led to a general bias within the hydrological community towards research on sites where the floodplain is a clear conduit for groundwater flow. In humid temperate regions of central Europe, floodplains have experienced rapid environmental changes since the last glaciation, yielding significant bedrock weathering and predominantly fine-grained, highly stratified hillslope and floodplain sediments. Such heterogeneous sedimentary architecture leads to conceptual ambiguities in the interpretation of the hydrogeological functioning of floodplains, thus raising the question: Do floodplains act as barriers or conduits to groundwater flow? This study analyzes the Ammer floodplain close to Tübingen in south-western Germany as a representative mid-section floodplain in a temperate climate where the regional bedrock-geology is dominated by mudstones. Geological, geophysical, and geochemical characterization and monitoring techniques were combined to shed light on the internal geological structure as a key control modulating the floodplain hydrology. Two partially separate groundwater systems were identified: a gravel body at the bottom of the Quaternary sediments and a Holocene confined tufaceous aquifer, separated by low-permeability clays. Despite flow being predominantly along-valley, sulfate concentrations in the floodplain aquifers showed evidence of a strong connection to the gypsum-bearing hillslope, particularly where tributary valley sediments are present (e.g., alluvial fans). Results from a floodplain water balance suggest the hillslope- and floodplain-aquifer material act as a barrier to hillslope groundwater recharge, where a large fraction may be bypassing the local floodplain groundwater system.

The stratification of sedimentary aquifers introduces spatial variability in hydraulic conductivity, primarily between individual horizontal layers. On larger scales, the vertical heterogeneity enhances hydraulic anisotropy, with the horizontal conductivity typically exceeding the vertical one. In this study, the hydraulic anisotropy of a stratified aquifer is estimated from data of hydraulic tests in which water is sequentially extracted from well sections screened at different depths, and the hydraulic response is measured at various multilevel observation wells. The applicability of the method is demonstrated by field tests in a fluvial gravel aquifer in the Upper Rhine Valley, Germany. A homogeneous anisotropic model, and models with three and five anisotropic layers, are fitted to the measured drawdowns in the steady-shape regime, in which differences in hydraulic head between observation locations do not change over time even though the head values themselves change. The position of the five horizontal layers is based on the lithology of the drilling profile at the pumping-well location. The three-layer model is achieved by merging insensitive or similar layers with sensitive layers. The fits result in estimates of the radial and vertical hydraulic conductivities for all layers of the respective models, which are upscaled to effective parameters over the entire depth in the case of the multilayer models. The homogeneous model shows significantly higher errors than those of the heterogeneous models. The heterogeneous locally anisotropic models not only reveal vertical variability of hydraulic conductivity, but also lead to a three-times larger anisotropy ratio upon upscaling.

We compare two ensemble Kalman-based methods to estimate the hydraulic conductivity field of an aquifer from data of hydraulic and tracer tomographic experiments: (i) the Ensemble Kalman Filter (EnKF) and (ii) the Kalman Ensemble Generator (KEG). We generated synthetic drawdown and tracer data by simulating two pumping tests, each followed by a tracer test. Parameter updating with the EnKF is performed using the full transient signal. For hydraulic data, we use the standard update scheme of the EnKF with damping, whereas for concentration data, we apply a restart scheme, in which solute transport is resimulated from time zero to the next measurement time after each parameter update. In the KEG, we iteratively assimilate all observations simultaneously, here inverting steady-state heads and mean tracer arrival times. The inversion with the dampened EnKF worked well for the transient pumping-tests, but less for the tracer tests. The KEG produced similar estimates of hydraulic conductivity but at significantly lower costs. We conclude that parameter estimation in well-defined hydraulic tests can be done very efficiently by iterative ensemble Kalman methods, and ambiguity between state and parameter updates can be completely avoided by assimilating temporal moments of concentration data rather than the time series themselves.

Sedimentary features can significantly influence flow and transport pathways in fine-grained valley fills. The spatial extent and properties of these features should be analyzed in order to determine residence times, flow pathways, and the reaction potential for contaminants. In the Ammer floodplain close to Tübingen, we examined peat layers and a gravel channel in order to determine their influence on the regional hydrogeology and hydrochemistry. Towards this end, we selected and combined geophysical and hydrogeological investigation techniques. Surface geoelectrical measurements revealed the spatial extent of relevant features, while subsequent borehole geophysical and direct-push surveys, including the in-situ detection of the sediment color, were used to assess their geometry and internal heterogeneity. At representative points, the hydraulic and biogeochemical properties of the sediments and the groundwater could be determined by targeted sampling and hydraulic tests. The general methodology of delineating relevant sub-units followed by high-resolution profiling may also be applied to investigate larger-scale valley fills.

Kurzfassung Sedimentäre Strukturen können die Fließ- und Stofftransportpfade in feinkörnigen Talfüllungen stark beeinflussen. Diese Strukturen müssen gezielt auf ihre Ausdehnung und Eigenschaften untersucht werden, um Verweilzeiten, Fließpfade und das Abbaupotenzial eingetragener Schadstoffe zu bestimmen. In der quartären Talfüllung der Ammeraue bei Tübingen wurden beispielhaft Torflagen und eine Kiesrinne untersucht, um ihre Einflüsse auf die regionale Hydrogeologie und Hydrochemie zu bewerten. Dafür wurden geophysikalische und hydrogeologische Erkundungsmethoden ausgewählt und kombiniert. Mit geoelektrischen Oberflächenmessungen konnte die Ausdehnung der betrachteten Strukturen erkundet werden. Unterschiedliche Direct-Push-Sondierungen, darunter eine In-situ-Bestimmung der Sedimentfarbe, und bohrlochgeophysikalische Messungen erfassten ihre Geometrie und interne Heterogenität. Die hydraulischen und biogeochemischen Eigenschaften der Sedimente und des Grundwassers wurden anschließend durch gezielte Probennahmen und hydraulische Tests an repräsentativen Ansatzpunkten bestimmt. Die dargestellte Methodenkombination zur Abgrenzung relevanter Teilgebiete mit anschließender hochauflösender Untersuchung lässt sich auch auf die Untersuchung großflächiger Täler übertragen.

The estimation of greenhouse gas emission rates from the subsurface into the atmosphere is an important part of climate-related research activities and associated efforts concerning the global carbon cycle. For the direct quantification of gas emission rates from the subsurface to the atmosphere a large variety of gas detection and flux quantification techniques exists. With the goal of measuring advective CO2 gas exhalations circumventing limitations of available systems such as e.g. accumulation-chamber systems or eddy-flux covariance methods, we developed a simple, robust, and low-cost gas-flow funnel system. The device allows for the continuous measurement of mass flow rates with a free, unrestricted gas flow from advectively dominated gas exhalation spots. For the design of the gas-flow funnel we used custom-made, though easy-to-produce components, and sensors that are typically already available when working at such sites. Our general design can easily be applied at sites with focused, advectively driven gas exhalation like volcanic areas, shale-gas seeps, landfills, and open boreholes. For the proof-of-concept we tested the system during three field campaigns at a site with natural CO2-bound emissions associated with a geologic fault in southwestern Germany. The measurements showed to be comparable and repeatable throughout the three campaigns, and are consistent with findings from other field sites with comparable CO2 exhalations.