Spatiotemporal scales of river-groundwater interaction - The role of local interaction processes and regional groundwater regimes.

Drinking water production in the vicinity of rivers not only requires the consideration of different spatiotemporal scales and settings of river-groundwater interaction processes, but also of local and regional scale groundwater regimes. Selected case studies in combination with field-experiments and the setup of high-resolution groundwater flow models enabled the investigation of the spatiotemporal development of microbial (classical fecal indicator bacteria and total cell counts) and selected organic micropollutants in riverine and regional groundwater for different hydrological settings, including low and high flow conditions. Proxy indicators suitable as surrogates for the diverse contaminations in alluvial aquifers with different settings could be identified. Based on the study results, the basic elements for both groundwater management and river restoration concepts are derived, which include the: (1) compilation and evaluation of the "current state" concerning hydrogeology, microbiology and contamination by organic micropollutants, (2) definition of field-experiments to qualitatively assess variability related to the "current state", and (3) quantitative assessment of groundwater regimes, including variability of groundwater components and inflow areas, by application of high-resolution groundwater flow models. The validity and transferability of the concept and inferred controls (specifically drivers and controls of river-groundwater interaction) are tested by evaluations derived from hydraulic relationships to river sections with comparable settings and regional groundwater flow regimes in general. The results of our investigations illustrate the influence of dynamic hydrologic boundary conditions on river-groundwater interaction and of regional scale groundwater flow regimes on the water composition of riverine groundwater systems. It is demonstrated how to identify river sections and their variations with intensified river-groundwater exchange processes and how to quantify the transient character of the different groundwater components that constitute the raw water quality of drinking water wells near rivers.

Comprehensive micropollutant screening using LC-HRMS/MS at three riverbank filtration sites to assess natural attenuation and potential implications for human health.

Riverbank filtration (RBF) is used worldwide to produce high quality drinking water. With river water often contaminated by micropollutants (MPs) from various sources, this study addresses the occurrence and fate of such MPs at three different RBF sites with oxic alluvial sediments and short travel times to the drinking water well down to hours. A broad range of MPs with various physico-chemical properties were analysed with detection limits in the low ng L-1 range using solid phase extraction followed by liquid chromatography coupled to tandem high resolution mass spectrometry. Out of the 526 MPs targeted, a total of 123 different MPs were detected above the limit of quantification at the three different RBF sites. Of the 75-96 MPs detected in each river, 43-59% were attenuated during RBF. The remaining total concentrations of the MPs in the raw drinking water accounted to 0.6-1.6 µgL-1 with only a few compounds exceeding 0.1 µgL-1, an often used threshold value. The attenuation was most pronounced in the first meters of infiltration with a full elimination of 17 compounds at all three sites. However, a mixing with groundwater related to regional groundwater flow complicated the characterisation of natural attenuation potentials along the transects. Additional non-target screening at one site revealed similar trends for further non-target components. Overall, a risk assessment of the target and estimated non-target compound concentrations finally indicated during the sampling period no health risk of the drinking water according to current guidelines. Our results demonstrate that monitoring of contamination sources within a catchment and the affected water quality remains important in such vulnerable systems with partially short residence times.

Characterization of a managed aquifer recharge system using multiple tracers.

Knowledge about the residence times of artificially infiltrated water into an aquifer and the resulting flow paths is essential to developing groundwater-management schemes. To obtain this knowledge, a variety of tracers can be used to study residence times and gain information about subsurface processes. Although a variety of tracers exists, their interpretation can differ considerably due to subsurface heterogeneity, underlying assumptions, and sampling and analysis limitations. The current study systematically assesses information gained from seven different tracers during a pumping experiment at a site where drinking water is extracted from an aquifer close to contaminated areas and where groundwater is artificially recharged by infiltrating surface water. We demonstrate that the groundwater residence times estimated using dye and heat tracers are comparable when the thermal retardation for the heat tracer is considered. Furthermore, major ions, acesulfame, and stable isotopes (δ2H and δ18O) show that mixing of infiltrated water and groundwater coming from the regional flow path occurred and a vertical stratification of the flow system exist. Based on the concentration patterns of dissolved gases (He, Ar, Kr, N2, and O2) and chlorinated solvents (e.g., tetrachloroethene), three temporal phases are observed in the ratio between infiltrated water and regional groundwater during the pumping experiment. Variability in this ratio is significantly related to changes in the pumping and infiltration rates. During constant pumping rates, more infiltrated water was extracted, which led to a higher dilution of the regional groundwater. An infiltration interruption caused however, the ratio to change and more regional groundwater is extracted, which led to an increase in all concentrations. The obtained results are discussed for each tracer considered and its strengths and limitations are illustrated. Overall, it is demonstrated that aquifer heterogeneity and various subsurface processes necessitate application of multiple tracers to quantify uncertainty when identifying flow processes.

Estimating the spatial distribution of artificial groundwater recharge using multiple tracers.

Stable isotopes of water, organic micropollutants and hydrochemistry data are powerful tools for identifying different water types in areas where knowledge of the spatial distribution of different groundwater is critical for water resource management. An important question is how the assessments change if only one or a subset of these tracers is used. In this study, we estimate spatial artificial infiltration along an infiltration system with stage-discharge relationships and classify different water types based on the mentioned hydrochemistry data for a drinking water production area in Switzerland. Managed aquifer recharge via surface water that feeds into the aquifer creates a hydraulic barrier between contaminated groundwater and drinking water wells. We systematically compare the information from the aforementioned tracers and illustrate differences in distribution and mixing ratios. Despite uncertainties in the mixing ratios, we found that the overall spatial distribution of artificial infiltration is very similar for all the tracers. The highest infiltration occurred in the eastern part of the infiltration system, whereas infiltration in the western part was the lowest. More balanced infiltration within the infiltration system could cause the elevated groundwater mound to be distributed more evenly, preventing the natural inflow of contaminated groundwater. Dedicated to Professor Peter Fritz on the occasion of his 80th birthday.

Nitrogen loss by anaerobic ammonium oxidation in unconfined aquifer soils.

Anaerobic ammonium oxidation (anammox) is recognized as an important process for nitrogen cycling, yet little is known about its role in the subsurface biosphere. In this study, we investigated the presence, abundance, and role of anammox bacteria in upland soil cores from Tianjin, China (20 m depth) and Basel, Switzerland (10 m depth), using isotope-tracing techniques, (q)PCR assays, and 16 S rRNA &hzsB gene clone libraries, along with nutrient profiles of soil core samples. Anammox in the phreatic (water-saturated) zone contributed to 37.5-67.6% of the N-loss (up to 0.675 gN m-2 d-1), with anammox activities of 0.005-0.74 nmolN g-1 soil h-1, which were even higher than the denitrification rates. By contrast, no significant anammox was measured in the vadose zone. Higher anammox bacterial cell densities were observed (0.75-1.4 × 107 copies g-1 soil) in the phreatic zone, where ammonia-oxidizing bacteria (AOB) maybe the major source of nitrite for anammox bacteria. The anammox bacterial cells in soils of the vadose zone were all <103 copies g-1 soil. We suggest that the subsurface provides a favorable niche for anammox bacteria whose contribution to N cycling and groundwater nitrate removal seems considerably larger than previously known.

Implications of hydrologic connectivity between hillslopes and riparian zones on streamflow composition.

Hydrological responses in mountainous headwater catchments are often highly non-linear with a distinct threshold-related behavior, which is associated to steep hillslopes, shallow soils and strong climatic variability. A holistic understanding of the dominant physical processes that control streamflow generation and non-linearity is required in order to assess potential negative effects of agricultural land use and water management in those areas. Therefore, streamflow generation in a small pre-Alpine headwater catchment (Upper Rietholzbach (URHB), ~1km(2)) was analyzed over a 2-year period by means of rainfall-response analysis and water quality data under explicit consideration of the joint behaviors of climate forcing and shallow groundwater dynamics. The runoff coefficients indicate that only a small fraction of the total catchment area (1-26%) generates streamflow during rainfall events. Hereby, the valley bottom areas (riparian zones) were the most important event-water source whereas only the lower parts of the hillslopes became hydrologically connected to the river network with higher antecedent moisture conditions. However, a distinct threshold-like behavior could not be observed, suggesting a more continuous shift from a riparian-zone to a more hillslope-dominated streamflow hydrograph. Regular manure application on the hillslopes in combinations with lateral hillslope groundwater flux and long groundwater residence times in the riparian zones resulted in a higher mineralization (e.g., total phosphorous) and significant denitrification in the valley bottom area. Despite the important role of the riparian zones for event-flow generation in the URHB, their nutrient buffer capacity is expected to be small due to the low permeability of the local subsurface material. The findings of this integrated analysis are summarized in a conceptual framework describing the hydrological functioning of hillslopes and riparian zones in the URHB.

Carry-over effects of the membrane interface probe.

The membrane interface probe (MIP) is widely used to characterize the subsurface distribution of volatile organic compounds (VOCs). One problem that arises during MIP application is that disproportionately high MIP signals are obtained after passing source zones which contain mobile or residual phases. This serious problem occurs because of a carry-over effect, in particular caused by compound-specific retention times in the conventional unheated transfer line, commonly used during such an investigation. The objective of this study was to perform a qualitative methodical field evaluation of the carry-over effect of a conventional MIP system with a conventional unheated transfer line. This was achieved by coupling a mobile mass spectrometer to the MIP device. Results obtained were then further compared with those achieved using a laser induced fluorescence (LIF) system. Because of this coupling, time- and depth-dependent signals for different substances became known. Field evaluation data obtained showed complex superpositions of compounds with MIP system results. As a result of this superposition, MIP signals from the saturated zone beneath the source zone (zone with free and/or residual phase) are blurred and are therefore not representative of particular depths. However, utilizing multidirectional probing alongside conventional MIP probing (forwards and backwards), it was possible to detect the upper and lower phase boundary of the source zone. These MIP results correlated excellently with the LIF results. An important conclusion that can be drawn from the field investigation is that coupling a mobile mass spectrometer to the MIP system enables advanced MIP signal interpretation to be successfully achieved.