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Alpine areas play a major role in water supply in downstream valleys by releasing water during warm and dry periods. However, the hydrogeology of alpine catchments, which are particularly exposed to the effects of climate change, is currently not well understood. Increasing our knowledge of alpine hydrogeological processes is thus of considerable importance for any forward‐looking hydrological investigations in alpine areas. The objectives of this study are to quantify seasonal groundwater storage variations in a small Swiss alpine catchment and to evaluate the capabilities of time‐lapse gravimetry in the identification of zones of high groundwater storage fluctuations. Time‐lapse gravimetric measurements enable rapid localisation of zones of dynamic groundwater storage changes and help to highlight aquifers with a higher storage decrease. Temperature sensors enable measurement of the temporal trend in stream and spring drying in the post‐snowmelt period. Stable isotope measurements allow us to identify the origin of surface water exiting the catchment. The results improve our comprehension of a conceptual schema highlighting two different hydrogeological systems: (a) a shallow, rapidly depleted one fed directly by snowmelt and (b) a deeper one, with a slower recession, fed by main recharge during peak snowmelt and emerging at the lower part of the catchment below the talus and moraine of the catchment where bedrock is exposed. These dynamics confirm the high variability of storage in the talus and moraine aquifers and highlight the dominant role of Quaternary deposits and their connectivity to store water over seasonal and multi‐year time‐scales. The mechanisms explaining the importance of Quaternary deposits are the combination of moraine and talus with different permeabilities allowing the storage of sufficient quantities of water permitting continuous release during drier periods of the year.

The effects of contaminant sources removal in 2005 (i.e. barrels, tank, pit and wastewater pipe sources) on carbon tetrachloride (CT) and chloroform (CF) concentration in groundwater were assessed at several areas of a fractured multi-contaminant aquifer (Odena, Spain) over a long-term period (2010–2014). Changes in redox conditions, in these chlorinated methanes (CMs) concentration and in their carbon isotopic compositions (δ13C) were monitored in multilevel wells. δ13C values from these wells were compared to those obtained from sources (barrels, tank and pit before their removal, 2002–2005) and to commercial solvents values in literature. Additionally, CMs natural attenuation processes were identified by C-Cl isotope slopes (Λ). Analyses revealed the downstream migration of the pollutant focus and an efficient removal of DNAPLs in the pit source's influence area. However, the removal of the contaminated soil from former tank and wastewater pipe was incomplete as leaching from unsaturated zone was proved, evidencing these areas are still active sources. Nevertheless, significant CMs degradation was detected close to all sources and Λ values pointed to different reactions. For CT in the tank area, Λ value fitted with hydrogenolysis pathway although other possible reduction processes were also uncovered. Near the wastewater pipe area, CT thiolytic reduction combined with hydrogenolysis was derived. The highest CT degradation extent accounted for these areas was 72 ± 11% and 84 ± 6%, respectively. For CF, the Λ value in the pit source's area was consistent with oxidation and/or with transport of CF affected by alkaline hydrolysis from upstream interception trenches. In contrast, isotope data evidenced CF reduction in the tank and wastewater pipe influence areas, although the observed Λ slightly deviates from the reference values, likely due to the continuous leaching of CF degraded in the non-saturated zone by a mechanism different from reduction.

Krypton-85 and other radioactive noble gases are widely used for groundwater dating purposes. 85Kr analysis require large volumes of water to reach the analytical requirements. Conventionally, this water is pumped to the surface to be degassed with a gas extraction system. The large pumping rate may disturb the natural flow field and requires substantial field logistics. Hence, we propose a new in-situ degassing method, in which membrane contactors are used to degas the groundwater directly in the well and gas is collected at the surface. This way, field work is facilitated, groundwater system disturbance is minimized, and the gas sample is collected at a specific depth. We demonstrate the tightness of the system regarding atmospheric air contamination for a collection times of 24 h, which is sufficient for both low-level counting and laser-based counting methods for 85Kr. The minimal borehole diameter is 7.5 cm for the prototype presented in this research but can easily be reduced to smaller diameters. In a case study, we compare the results obtained with the new passive method with those from a conventional packer setup sampling. Additionally, 3H/3He samples were collected for both sampling regimes and the dating results were compared with those from 85Kr. A good agreement between tracer ages is demonstrated and the age stratigraphy is consistent with the expected age distribution for a porous unconfined aquifer. In addition, our study emphasizes the differences between the age information sampled with various methods. In conclusion, we demonstrate that the new in situ quasi-passive method provides a more representative age stratigraphy with depth in most cases.

Snowfall is the dominant form of precipitation in high mountainous areas and its driving melt water has an indispensable role in the hydrological cycle and groundwater recharge, particularly in karstic landscapes with high infiltration capacity. Monitoring snow cover area (SCA) and its melting process is essential for the investigation of climatic variables, hydrology, hydrogeology, and water resource management. Prodigious advances of satellite imaginary technology in the past decades made it possible to monitor spatiotemporal distribution of snow and its melting process. In this research, SCA was investigated using cloud-free images of Landsat-8 from December 2014 to June 2016 and Sentinel-2 from November 2015 to June 2016 at Lasem area (north of Iran) by normalized difference snow index. Simultaneously, the discharges of the main karstic springs were monitored over May 2015 to June 2016. The catchment subdivided into three sub-zones based on the hydrogeological characteristics and snow melting time. Fractional SCA time series within each subdomain used to develop snow melting curve in each subzone. Comparison of melting peaks between the 2014–2015 and 2015–2016 water years shows that melting shifted in average 20 days later in 2016 at north-facing subdomains. North-facing slopes show quite fast transmitting time (20–35 days) of the peak snowmelt to the springs, while the south-facing springs are more silent to the recharge pulses (70–80 days), indicating a higher degree of karstification in north-facing domains. More concentrated snowmelt in 2016 led to increasing peak flow by an average of 15% in the springs fed by north-facing domains.

Knowing how stream discharge in an ungauged catchment reacts to dry spells is a major challenge for managing water resources. The role of geology on these dynamics is poorly understood. For the Swiss Molasse basin, we therefore explored how the geology influences the groundwater contribution to stream flow during low-flow conditions. Using existing data from geological reports and maps as well as from deep boreholes, we constructed a basin-wide overview of the hydrogeological quality of the bedrock and investigated five catchments in 3D. We found that catchments with the most permeable sedimentary bedrock are least sensitive to low flows (marine sandstone, K = 10&minus, 4 to 10&minus, 5 m/s, Peff = 5&ndash, 10%). In contrast, if bedrock K is low (K &lt, 10&minus, 6 m/s), the presence of a productive Quaternary volume becomes decisive for groundwater contribution to stream flow. Limitations exist due to a restricted database for K and Peff values of the Molasse and limited information on continuation of lithologies with depth. This emphasizes the need for more hydrogeologically relevant data for the future management of water resources. Our results highlighting what lithotypes favor groundwater contribution to stream flow are valid also in other regions for the assessment of a catchment&rsquo, s sensitivity to low flows.

Relating stream dynamics to catchment properties is essential to anticipate the influence of changing environmental conditions and to predict flows of ungauged rivers. Although the importance of subsurface processes in catchment hydrology is widely acknowledged, geological characteristics are rarely explicitly included in studies assessing physiographic controls on catchment dynamics. In this investigation of 22 catchments of the Swiss Plateau and Prealpes, we use a simple linear regression approach to analyze the relationship between streamflow indicators and various geological and hydrogeological properties of the bedrock and quaternary deposits, along with meteorological, soil, land use and topographical characteristics. We use long-term discharge percentiles, as well as dimensionless flow duration curves (FDC, standardized by long-term mean discharge) that allow to evaluate the catchment response to climate forcing. While climate conditions dominate the high to medium discharge percentiles (Q5–Q50), the capacity of the catchments to buffer the meteorological forcing can only be attributed to geological characteristics. The sandstone proportion in the catchments explains 54% of the variance of both extremities of the dimensionless FDC (Q5/Qmean and Q95/Qmean) and productive quaternary deposits are responsible of 55% resp. 58% of the variance of the two ratios. Examining the hydrogeological characteristics of both bedrock and quaternary lithologies considerably improves the understanding of catchment dynamics.

Stable isotopes oxygen-18 (δ18O) and deuterium (δD) and the hydrochemistry of the main springs of well-developed karst aquifers in Lar watershed in the Haraz basin, northern Iran, were investigated. Water samples were collected in the recession period for analysis of major ions and the stable isotopes. Predominant hydrochemical types of main karst springs samples were Ca2+ – Mg2+ – $$ {\mathrm{HCO}}_3^{-} $$ type. The hydrochemical composition of the karst springs is dominated by Ca2+, Mg2+, $$ {\mathrm{HCO}}_3^{-} $$ and $$ {\mathrm{SO}}_4^{2-} $$ ions. The hydrochemical results indicate that dissolution of carbonate rocks (limestone and dolomite) governs the major ion concentrations, with minor effects of silicate weathering, ion exchange and precipitation effects on concentrations of Na+, Cl−, K+, and $$ {\mathrm{SO}}_4^{2-} $$ . In the northern parts of the study area, hydrothermal fluid affects the chemistry of the draining springs. The isotopic content ranges from −43.8 to −52.9‰ and from −7.09 to −8.97‰ for δD and δ18O, respectively. The karst spring samples lie above the local meteoric water line, similar to the δ18O and δD signature of the snowpack samples, and have small spatial and temporal variability. The similarity of the isotopic composition of the springs to the snowpack suggests that the dominant recharge is by snowmelt water.

Dense non-aqueous phase liquids (DNAPLs) can easily penetrate into karst aquifers, may accumulate in the sediment-filled depressions of conduits, and constitute a long-term source of groundwater contamination. In contrast to porous media, DNAPL dissolution in karst settings has not received much attention. This study investigated the dissolution of sediment-entrapped DNAPLs using a laboratory analogue model corresponding to a syphon structure partly filled by sediments and using numerical simulations. The mass transfer rate increased with an increasing conduit Reynolds number (Re) and increasing conduit angle, as both of these factors led to a more intense hyporheic flow in the sediments. In addition, the mass transfer rate increased linearly with the average flow velocity in the sediment and was higher than expected for an infinite porous medium considered as a reference case. The enhanced mass transfer rate can be explained by the curved streamlines associated with hyporheic flow, which transport solutes away from the DNAPL interface. This study demonstrates that hyporheic flow through karst sediment is a possible mechanism for the mobilization of DNAPL components and might explain the persistent occurrence of such contaminants in karst springs.

This modeling study aims to investigate how reactive processes in aquitards impact plume persistence in adjacent aquifers. For that purpose the migration of a trichloroethene (TCE) plume in an aquifer originating from dense non-aqueous phase liquid (DNAPL) source dissolution and back-diffusion from an underlying reactive aquitard was simulated in a 2D-numerical model. Two aquitard degradation scenarios were modeled considering one-step degradation from TCE to cis-dichloroethene (cDCE): a uniform (constant degradation with aquitard depth) and a non-uniform scenario (decreasing degradation with aquitard depth) and were compared with a no-degradation scenario. In the no-degradation scenario, a long-term TCE tailing above the Maximum Contaminant Level (MCL) caused by back-diffusion after source removal was observed. In contrast, in the aquitard degradation scenarios, TCE back-diffusion periods were shorter, whereby the extent of back-diffusion reduction depended on the aquitard degradation depth and the rate. For high degradation rates (half-life: 30-80days), an aquitard degradation depth greater than 65cm prevented TCE plume persistence after source removal but generated a long-term tailing above the MCL for the produced cDCE. For slow degradation rates (half-life:200days), TCE was only partially degraded after source removal, independent of the aquitard degradation depth, leading to a long-term dual contamination of the aquifer by cDCE and TCE. A sudden enrichment of

Groundwater quality in many regions with intense agriculture has deteriorated due to the leaching of nitrate and other agricultural pollutants. Modified agricultural practices can reduce the input of nitrate to groundwater bodies, but it is crucial to determine the time span over which these measures become effective at reducing nitrate levels in pumping wells. Such estimates can be obtained from hydrogeological modeling or lumped-parameter models (LPM) in combination with environmental tracer data. Two challenges in such tracer-based estimates are (i) accounting for the different modes of transport in the unsaturated zone (USZ), and (ii) assessing uncertainties. Here we extend a recently published Bayesian inference scheme for simple LPMs to include an explicit USZ model and apply it to the Dunnerngau aquifer, Switzerland. Compared to a previous estimate of travel times in the aquifer based on a 2D hydrogeological model, our approach provides a more accurate assessment of the dynamics of nitrate concentrations in the aquifer. We find that including tracer measurements (3H/3He, 85Kr, 39Ar, 4He) reduces uncertainty in nitrate predictions if nitrate time series at wells are not available or short, but does not necessarily lead to better predictions if long nitrate time series are available. Additionally, the combination of tracer data with nitrate time series allows for a separation of the travel times in the unsaturated and saturated zone.

Alluvial aquifers in mountainous regions cover typically a limited area. Their contribution to catchment storage and outflow is rarely isolated; alluvial groundwater discharge under gauging stations is generally assumed negligible; and hydrological models tend to lump alluvial storage with other units. The role of alluvial aquifers remains therefore unclear: can they contribute significantly to outflow when they cover a few percent of catchment area? Should they be considered a dynamic storage unit or merely a transmission zone? We address these issues based on the continuous monitoring of groundwater discharge, river discharge (one year), and aquifer storage (6 months) in the 6 km2 alluvial system of a 194 km2 catchment. River and groundwater outflow were measured jointly through “coupled gauging stations.” The contribution of alluvial groundwater to outflow was highest at the outlet of a subcatchment (52 km2), where subsurface discharge amounted to 15% of mean annual outflow, and 85% of outflow during the last week of a drought. In this period, alluvial-aquifer depletion supported 75% of the subcatchment outflow and 35% of catchment outflow—thus 3% of the entire catchment supported a third of the outflow. Storage fluctuations occurred predominantly in the aquifer's upstream part, where heads varied over 6 m. Not only does this section act as a significant water source, but storage recovers also rapidly at the onset of precipitation. Storage dynamics were best conceptualized along the valley axis, rather than across the more conventional riparian-channel transect. Overall the contribution of alluvial aquifers to catchment outflow deserves more attention.

The persistence of groundwater contaminants is influenced by several interacting processes. Physical, physico-chemical, and (bio-)chemical processes all influence the transport of contaminants in the subsurface. However, for a given hydrogeological system, it is generally unclear to which degree each of these phenomena acts as a control on plume behaviour. Here, we present a comprehensive investigation of these processes and their influences on plume behaviour and persistence in layered sedimentary systems. We investigate different scenarios that represent fundamental configurations of common contaminant situations. A confined aquifer over- and underlain by aquitard layers is investigated in a source-removal scenario and a constant-source equilibrium scenario. Additionally, an aquitard overlain and underlain by high permeability units is investigated in a source-removal scenario. In these investigations, we vary layer thickness, as well as parameters governing advection, (back-)diffusion, sorption, and degradation. Extensive analysis of these results enables quantification of the influence of these parameters on maximum down-gradient concentration, plume persistence duration, and plume spatial extent. Finally, parameter space dimensionality reduction is used to establish trends and regimes in which certain processes dominate as controls. A lower limit to plume extent as a function of a novel constructed parameter is also determined. These results provide valuable quantitative information for the assessment of the fate of groundwater contaminants and are applicable to a wide range of aqueous-phase solutes.

Chloroform has been for a long time considered only as an anthropogenic contaminant. The presence of chloroform in forest soil and groundwater has been widely demonstrated. The frequent detection of chloroform in groundwater in absence of other contaminants suggests that chloroform is likely produced naturally. Compound-specific isotope analysis of chloroform was performed on soil-gas and groundwater samples to elucidate whether its source is natural or anthropogenic. The δ13C values of chloroform (−22.8 to −26.2‰) present in soil gas collected in a forested area are within the same range as the soil organic matter (−22.6 to −28.2‰) but are more enriched in 13C compared to industrial chloroform (−43.2 to −63.6‰). The δ13C values of chloroform at the water table (−22.0‰) corresponded well to the δ13C of soil gas chloroform, demonstrating that the isotope signature of chloroform is maintained during transport through the unsaturated zone. Generally, the isotope signature of chloroform is conserved also during longer range transport in the aquifer. These δ13C data support the hypothesis that chloroform is naturally formed in some forest soils. These results may be particularly relevant for authorities’ regulation of chloroform which in the case of Denmark was very strict for groundwater (

Groundwater recharge from snowmelt represents a temporal redistribution of precipitation. This is extremely important because the rate and timing of snowpack drainage has substantial consequences to aquifer recharge patterns, which in turn affect groundwater availability throughout the rest of the year. The modeling methods developed to estimate drainage from a snowpack, which typically rely on temporally-dense point-measurements or temporally-limited spatially-dispersed calibration data, range in complexity from the simple degree-day method to more complex and physically-based energy balance approaches. While the gamut of snowmelt models are routinely used to aid in water resource management, a comparison of snowmelt models’ predictive uncertainties had previously not been done. Therefore, we established a snowmelt model calibration dataset that is both temporally dense and represents the integrated snowmelt infiltration signal for the Vers Chez le Brandt research catchment, which functions as a rather unique natural lysimeter. We then evaluated the uncertainty associated with the degree-day, a modified degree-day and energy balance snowmelt model predictions using the null-space Monte Carlo approach. All three melt models underestimate total snowpack drainage, underestimate the rate of early and midwinter drainage and overestimate spring snowmelt rates. The actual rate of snowpack water loss is more constant over the course of the entire winter season than the snowmelt models would imply, indicating that mid-winter melt can contribute as significantly as springtime snowmelt to groundwater recharge in low alpine settings. Further, actual groundwater recharge could be between 2 and 31% greater than snowmelt models suggest, over the total winter season. This study shows that snowmelt model predictions can have considerable uncertainty, which may be reduced by the inclusion of more data that allows for the use of more complex approaches such as the energy balance method. Further, our study demonstrated that an uncertainty analysis of model predictions is easily accomplished due to the low computational demand of the models and efficient calibration software and is absolutely worth the additional investment. Lastly, development of a systematic instrumentation that evaluates the distributed, temporal evolution of snowpack drainage is vital for optimal understanding and management of cold-climate hydrologic systems.

A diesel fuel contaminated aquifer in Menziken, Switzerland was treated for 4.5 years by injecting aerated groundwater, supplemented with KNO3 and NH4H2PO4 to stimulate indigenous populations of petroleum hydrocarbon (PHC) degrading microorganisms. After dissolved PHC concentrations had stabilized at a low level, engineered in situ bioremediation was terminated. The main objective of this study was to evaluate the efficacy of intrinsic in situ bioremediation as a follow-up measure to remove PHC remaining in the aquifer after terminating engineered in situ bioremediation. In the first 7 months of intrinsic in situ bioremediation, redox conditions in the source area became more reducing as indicated by lower concentrations of SO24‾ and higher concentrations of Fe(II) and CH4. In the core of the source area, strongly reducing conditions prevailed during the remaining study period (3 years) and dissolved PHC concentrations were higher than during engineered in situ bioremediation. This suggests that biodegradation in the core zone was limited by the availability of oxidants. In lateral zones of the source area, however, gradually more oxidized conditions were reestablished again, suggesting that PHC availability increasingly limited biodegradation. The total DIC production rate in the aquifer decreased within 2 years to about 25% of that during engineered in situ bioremediation and remained at that level. Stable carbon isotope analysis confirmed that the produced DIC mainly originated from PHC mineralization. The total rate of DIC and CH4 production in the source area was more than 300 times larger than the rate of PHC elution. This indicates that biodegradation coupled to consumption of naturally occurring oxidants was an important process for removal of PHC which remained in the aquifer after terminating engineered measures.

Summary Even though karstic aquifers are important freshwater resources and frequently occur in mountainous areas, recharge processes related to snowmelt have received little attention thus far. Given the context of climate change, where alterations to seasonal snow patterns are anticipated, and the often-strong coupling between recharge and discharge in karst aquifers, this research area is of great importance. Therefore, we investigated how snowmelt water transits through the vadose and phreatic zone of a karst aquifer. This was accomplished by evaluating the relationships between meteorological data, soil–water content, vadose zone flow in a cave 53 m below ground and aquifer discharge. Time series data indicate that the quantity and duration of meltwater input at the soil surface influences flow and storage within the soil and epikarst. Prolonged periods of snowmelt promote perched storage in surficial soils and encourage surficial, lateral flow to preferential flow paths. Thus, in karstic watersheds overlain by crystalline loess, a typical pedologic and lithologic pairing in central Europe and parts of North America, soils can serve as the dominant mechanism impeding infiltration and promoting shallow lateral flow. Further, hydrograph analysis of vadose zone flow and aquifer discharge, suggests that storage associated with shallow soils is the dominant source of discharge at time scales of up to several weeks after melt events, while phreatic storage becomes import during prolonged periods without input. Soils can moderate karst aquifer dynamics and play a more governing role on karst aquifer storage and discharge than previously credited. Overall, this signifies that a fundamental understanding of soil structure and distribution is critical when assessing recharge to karstic aquifers, particularly in cold regions.

When implementing remediation programs to mitigate diffuse-source contamination of aquifers, tools are required to anticipate if the measures are sufficient to meet groundwater quality objectives and, if so, in what time frame. Transfer function methods are an attractive approach, as they are easier to implement than numerical groundwater models. However, transfer function approaches as commonly applied in environmental tracer studies are limited to a homogenous input of solute across the catchment area and a unique transfer compartment. The objective of this study was to develop and test an original approach suitable for the transfer of spatially varying inputs across multiple compartments (e.g. unsaturated and saturated zone). The method makes use of a double convolution equation accounting for transfer across two compartments separately. The modified transfer function approach was applied to the Wohlenschwil aquifer (Switzerland), using a formulation of the exponential model of solute transfer for application to subareas of aquifer catchments. A minimum of information was required: (1) delimitation of the capture zone of the outlet of interest; (2) spatial distribution of historical and future pollution input within the capture zone; (3) contribution of each subarea of the recharge zone to the flow at the outlet; (4) transfer functions of the pollutant in the aquifer. A good fit to historical nitrate concentrations at the pumping well was obtained. This suggests that the modified transfer function approach is suitable to explore the effect of environmental projects on groundwater concentration trends, especially at an early screening stage.

This field and modeling study aims to reveal if degradation of chlorinated hydrocarbons in low permeability sediments can be quantified using compound-specific isotope analysis (CSIA). For that purpose, the well-characterized Borden research site was selected, where an aquifer-aquitard system was artificially contaminated by a three component chlorinated solvent mixture (tetrachloroethene (PCE) 45 vol %, trichloroethene (TCE) 45 vol %, and chloroform (TCM) 10 vol %). Nearly 15 years after the contaminant release, several high-resolution concentration and CSIA profiles were determined for the chlorinated hydrocarbons that had diffused into the clayey aquitard. The CSIA profiles showed large shifts of carbon isotope ratios with depth (up to 24‰) suggesting that degradation occurs in the aquitard despite the small pore sizes. Simulated scenarios without or with uniform degradation failed to reproduce the isotope data, while a scenario with decreasing degradation with depth fit the data well. This suggests that nutrients had diffused into the aquitard favoring stronger degradation close to the aquifer-aquitard interface than with increasing depth. Moreover, the different simulation scenarios showed that CSIA profiles are more sensitive to different degradation conditions compared to concentration profiles highlighting the power of CSIA to constrain degradation activities in aquitards.

Integrated catchment-scale management approaches in large catchments are often hindered due to the poor understanding of the spatially and seasonally variable pathways of pollutants. High-frequency monitoring of water quality at random locations in a catchment is resource intensive and challenging. A simplified catchment-scale monitoring approach is developed in this study, for the preliminary identification of water quality changes – Integrated spatial snap-shot monitoring (ISSM). This multi-parameter monitoring approach is applied using the isotopes of water (δ18O-H2O and δD) and nitrate (δ15N-NO ‾3 and δ18O-NO‾3) together with the fluxes of nitrate and other solutes, which are used as chemical markers. This method involves selection of few sampling stations, which are identified as the hotspots of water quality changes within the catchment. The study was conducted in the peri-alpine Thur catchment in Switzerland, with two snap-shot campaigns (representative of two widely varying hydrological conditions), in summer 2012 (low flow) and spring 2013 (high flow). Significant spatial (varying with elevation) and seasonal changes in the sources of water were observed between the two seasons. A spatial variation of the sources of nitrate and the solute loads was observed, in tandem with the land use changes in the Thur catchment. There is a seasonal shift in the sources of nitrate, it varies from a strong treated waste water signature during the low flow season to a mixture of other sources (like soil nitrogen derived from agriculture), in the high flow season. This demonstrates the influence of other sources that override the influence of waste water treatment plants (WWTPs) during high flow in the Thur River and its tributaries. This method is expected to be a cost-effective alternative, providing snap-shots, that can help in the preliminary identification of the pathways of solutes and their seasonal/spatial changes in catchments.

International audience; Crystalline aquifers of semi-arid southern India represent a vital water resource for farming communities. A field study is described that characterizes the hydrodynamic functioning of intensively exploited crystalline aquifers at local scale based on detailed well monitoring during one hydrological year. The main results show large water-table fluctuations caused by monsoon recharge and pumping, high spatial variability in well discharges, and a decrease of well yields as the water table decreases. Groundwater chemistry is also spatially variable with the existence of aquifer compartments within which mixing occurs. The observed variability and compartmentalization is explained by geological heterogeneities which play a major role in controlling groundwater flow and connectivity in the aquifer. The position of the water table within the fracture network will determine the degree of connectivity between aquifer compartments and well discharge. The presented aquifer conceptual model suggests several consequences: (1) over-exploitation leads to a drop in well discharge, (2) intensive pumping may contribute to the hydraulic containment of contaminants, (3) groundwater quality is highly variable even at local scale, (4) geological discontinuities may be used to assist in the location of drinking-supply wells, (5) modeling should integrate threshold effects due to water-table fluctuations.

Virus inactivation and virus adsorption, resulting from interactions with minerals, constitute important aspects of an aquifers disinfection capacity. Investigations using a 20 cm column filled with medium-grained natural sands demonstrated that the sands can attenuate up to 62% of a pulse of viruses injected. Experiments using repeatedly washed sands had significantly lower attenuation capacity than fresh sands, due to removal of fine-grained (silt and clay-sized) coatings on grain surfaces. X-ray diffraction analyses of the sand, and the associated fine-grained coating indicated that no significant mineralogical differences existed between these two materials. The experimental data suggested that rougher surfaces/crystal edges in the grain coatings reduced repulsive forces between viruses and the sands permitting greater virus adsorption to the column matrix. Soaking all sands with Tryptone solution after testing released adsorbed viruses indicated that short-term viral inactivation due to interactions with the column matrix was a negligible part of the attenuation process.

An economical multilevel groundwater monitoring system has been developed that can be rapidly installed with a direct-push machine, yet is suitable for sampling across large permeability contrasts. This sealed multiport sampling (SMPS) system consists of up to five lengths of PVC tubing (12 mm OD), each with a screen at a specific depth created by drilling 2.5-mm holes. Above and below each screen, round elastomer pieces, with peripheral holes (to clip in the sampling tubes) and a central hole (to hold a discontinuous piece of central tubing at the height of the screen), are emplaced. Cement-bentonite grout is injected via a tremie tube inserted through the discontinuous centre tube into each interval between the sampling screens. The elastomer pieces and central tube prevent grout from reaching the screened interval. A textile wrapped around the system holds the arrangement in place and at the same time serves to filter the groundwater at the level of the sampling screens. The SMPS system was tested at a tetrachloroethene (PCE) contaminated site. The seals effectively separated the sampling intervals even in heterogeneous formations. Furthermore, concentration profiles agreed well with a reference system. The system should be suitable for a wide range of hydrogeological conditions.

Permanganate injection is increasingly applied for in situ destruction of chlorinated ethenes in groundwater. This laboratory and field study demonstrates the roles that carbon isotope analysis can play in the assessment of oxidation of trichloroethene (TCE) by permanganate. In laboratory experiments a strong carbon isotope fractionation was observed during oxidation of TCE with similar isotopic enrichment factors (−25.1 to −26.8 ‰) for initial KMnO4 concentrations between 67 and 1250 mg/L. At the field site, a single permanganate injection episode was conducted in a sandy aquifer contaminated with TCE as dense nonaqueous liquid (DNAPL). After injection, enriched δ13C values of up to +204% and elevated Cl- concentrations were observed at distances of up to 4 m from the injection point. Farther away, the Cl- increased without any change in δ13C of TCE suggesting that Cl- was not produced locally but migrated to the sampling point. Except for the closest sampling location to the injection point, the δ13C rebounded to the initial δ13C again, likely due to dissolution of DNAPL. Isotope mass balance calculations made it possible to identify zones where TCE oxidation continued to occur during the rebound phase. The study indicates that δ13C values can be used to assess the dynamics between TCE oxidation and dissolution and to locate zones of oxidation of chlorinated ethenes that cannot be identified from the Cl- distribution alone.

Summary Karst conduits are often partly filled by clastic sediments. Flow through such sediments can have a strong impact on the fate of sediment-entrapped contaminants. In contrast to stream bed sediments, hyporheic flow in karst sediments has received little attention so far. For karst sediments, conduit bends could induce hyporheic flow, in addition to bedforms or obstacles. The main aim of this study was to investigate flow processes in a conduit-sediment system using a laboratory model resembling a siphon and numerical modeling. In the laboratory system, zones with forward and reserve flow occurred in the sediment due to the conduit bends. As demonstrated with sediment-source tracer test, entrapped solutes were generally flushed out more rapidly at a higher flow rate and steeper conduit angle. Numerical modeling assuming pressure continuity across the conduit-sediment interface reproduced the flow patterns and breakthrough curves (BTCs) well. Based on the model, the magnitude of hyporheic exchange is expected to increase linearly with the flow rate and was higher for a steeper conduit angle. However, the increase in flushing intensity was not evenly distributed throughout the sediments but occurred mainly adjacent to the conduit bends consistent with observations from tracer tests. This study confirms that conduit bends could have a strong influence on hyporheic flow in karst sediments.

The spatial distribution and temporal dynamics of a benzene plume in an alluvial aquifer strongly affected by river fluctuations was studied. Benzene concentrations, aquifer geochemistry datasets, past river morphology, and benzene degradation rates estimated in situ using stable carbon isotope enrichment were analyzed in concert with aquifer heterogeneity and river fluctuations. Geochemistry data demonstrated that benzene biodegradation was on-going under sulfate reducing conditions. Long-term monitoring of hydraulic heads and characterization of the alluvial aquifer formed the basis of a detailed modeled image of aquifer heterogeneity. Hydraulic conductivity was found to strongly correlate with benzene degradation, indicating that low hydraulic conductivity areas are capable of sustaining benzene anaerobic biodegradation provided the electron acceptor (SO4 2‐ ) does not become rate limiting. Modeling results demonstrated that the groundwater flux direction is reversed on annual basis when the river level rises up to 2m, thereby forcing the infiltration of oxygenated surface water into the aquifer. The mobilization state of metal trace elements such as Zn, Cd, and As present in the aquifer predominantly depended on the strong potential gradient within the plume. However, infiltration of oxygenated water was found to trigger a change from strongly reducing to oxic conditions near the river, causing mobilization of previously immobile metal species and vice versa. MNA appears to be an appropriate remediation strategy in this type of dynamic environment provided that aquifer characterization and targeted monitoring of redox conditions are adequate and electron acceptors remain available until concentrations of toxic compounds reduce to acceptable levels.

Compound-specific isotope analysis (CSIA) is a powerful tool to track contaminant fate in groundwater. However, the application of CSIA to chlorinated ethanes has received little attention so far. These compounds are toxic and prevalent groundwater contaminants of environmental concern. The high susceptibility of chlorinated ethanes like 1,1,1-trichloroethane (1,1,1-TCA) to be transformed via different competing pathways (biotic and abiotic) complicates the assessment of their fate in the subsurface. In this study, the use of a dual C-Cl isotope approach to identify the active degradation pathways of 1,1,1- TCA is evaluated for the first time in an aerobic aquifer impacted by 1,1,1-TCA and trichloroethylene (TCE) with concentrations of up to 20 mg/L and 3.4 mg/L, respectively. The reaction-specific dual carbon-chlorine (C-Cl) isotope trends determined in a recent laboratory study illustrated the potential of a dual isotope approach to identify contaminant degradation pathways of 1,1,1-TCA. Compared to the dual isotope slopes (Δδ13C/Δδ37CI) previously determined in the laboratory for dehydrohalogenation/hydrolysis (DH/HY, 0.33 ± 0.04) and oxidation by persulfate (∞), the slope determined from field samples (0.6 ± 0.2, r2 = 0.75) is closer to the one observed for DH/HY, pointing to DH/HY as the predominant degradation pathway of 1,1,1-TCA in the aquifer. The observed deviation could be explained by a minor contribution of additional degradation processes. This result, along with the little degradation of TCE determined from isotope measurements, confirmed that 1,1,1-TCA is the main source of the 1,1-dichlorethylene (1,1-DCE) detected in the aquifer with concentrations of up to 10 mg/L. This study demonstrates that a dual C-Cl isotope approach can strongly improve the qualitative and quantitative assessment of 1,1,1-TCA degradation processes in the field.

Aquifers provide water, nutrients and energy with various patterns for many aquatic and terrestrial ecosystems. Groundwater-dependent ecosystems (GDEs) are increasingly recognized for their ecological and socio-economic values. The current knowledge of the processes governing the ecohydrological functioning of inland GDEs is reviewed, in order to assess the key drivers constraining their viability. These processes occur both at the watershed and emergence scale. Recharge patterns, geomorphology, internal geometry and geochemistry of aquifers control water availability and nutritive status of groundwater. The interface structure between the groundwater system and the biocenoses may modify the groundwater features by physicochemical or biological processes, for which biocenoses need to adapt. Four major types of aquifer-GDE interface have been described: springs, surface waters, peatlands and terrestrial ecosystems. The ecological roles of groundwater are conditioned by morphological characteristics for spring GDEs, by the hyporheic zone structure for surface waters, by the organic soil structure and volume for peatland GDEs, and by water-table fluctuation and surface floods in terrestrial GDEs. Based on these considerations, an ecohydrological classification system for GDEs is proposed and applied to Central and Western-Central Europe, as a basis for modeling approaches for GDEs and as a tool for groundwater and landscape management.

Compound-specific isotope analysis (CSIA) can potentially be used to relate vapor phase contamination by volatile organic compounds (VOCs) to their subsurface sources. This field and modeling study investigated how isotope ratios evolve during migration of gaseous chlorinated ethenes across a 18 m thick unsaturated zone of a sandy coastal plain aquifer. At the site, high concentrations of tetrachloroethene (PCE up to 380 µg/L), trichloroethene (TCE up to 31,600 µg/L), and cis-1,2-dichloroethene (cDCE up to 680 µg/L) were detected in groundwater. Chlorinated ethene concentrations were highest at the water table and steadily decreased upward toward the land surface and downward below the water table. Although isotopologues have different diffusion coefficients, constant carbon and chlorine isotope ratios were observed throughout the unsaturated zone, which corresponded to the isotope ratios measured at the water table. In the saturated zone, TCE became increasingly depleted along a concentration gradient, possibly due to isotope fractionation associated with aqueous phase diffusion. These results indicate that carbon and chlorine isotopes can be used to link vapor phase contamination to their source even if extensive migration of the vapors occurs. However, the numerical model revealed that constant isotope ratios are only expected for systems close to steady state.

Summary This study investigated the use of radon (222Rn), a radioactive isotope with a half-life of 3.8 days, and CO2 as natural tracers to evaluate the recharge dynamics of karst aquifer under varying hydrological conditions. Dissolved 222Rn and carbon dioxide (CO2) were measured continuously in an underground stream of the Milandre test site, Switzerland. Estimated soil water 222Rn activities were higher than baseflow 222Rn activities, indicating elevated 222Rn production in the soil zone compared to limestone, consistent with a 226Ra enrichment in the soil zone compared to limestone. During small flood events, 222Rn activities did not vary while an immediate increase of the CO2 concentration was observed. During medium and large flood events, an immediate CO2 increase and a delayed 222Rn activity increase to up to 4.9 Bq/L and 11 Bq/L, respectively occurred. The detection of elevated 222Rn activities during medium and large flood events indicate that soil water participates to the flood event. A soil origin of the 222Rn is consistent with its delayed increase compared to discharge reflecting the travel time of 222Rn from the soil to the saturated zone of the system via the epikarst. A three-component mixing model suggested that soil water may contribute 4–6% of the discharge during medium flood events and 25–43% during large flood events. For small flood events, the water must have resided at least 25 days below the soil zone to explain the background 222Rn activities, taking into account the half-life of 222Rn (3.8 days). In contrast to 222Rn, the CO2 increase occurred simultaneously with the discharge increase. This observation as well as the CO2 increase during small flood events, suggests that the elevated CO2 level is not due to the arrival of soil water as for 222Rn. A possible explanation for the CO2 trend is that baseflow water in the stream has lower CO2 levels due to gas loss compared to water stored in low permeability zones. During flood event, the stored water is more rapidly mobilised than during baseflow with less time for gas loss. The study demonstrates that 222Rn and CO2 provides value information on the dynamics of groundwater recharge of karst aquifer, which can be of high interest when evaluating the vulnerability of such systems to contamination.

The original version of this article unfortunately contained a mistake. The spelling of the 3rd author’s name was incorrect. The correct spelling is given above. The publisher regrets this mistake. The original article has been corrected.

Field and laboratory investigations have been conducted at a former coke plant, in order to assess pollutant attenuation in a contaminated alluvial aquifer, discharging to an adjacent river. Various organic (BTEX, PAHs, mineral oils) and inorganic (As, Zn, Cd) compounds were found in the aquifer in concentrations exceeding regulatory values. Due to redox conditions of the aquifer, heavy metals were almost immobile, thus not posing a major risk of dispersion off-site the brownfield. Field and laboratory investigations demonstrated that benzene, among organic pollutants, presented the major worry for off-site dispersion, mainly due to its mobility and high concentration, i.e. up to 750 mg L-1 in the source zone. However, benzene could never be detected near the river which is about 160 m downgradient the main source. Redox conditions together with benzene concentrations determined in the aquifer have suggested that degradation mainly occurred within 100 m distance from the contaminant source under anoxic conditions, and most probably with sulphate as main oxidant. A numerical groundwater flow and transport model, calibrated under transient conditions, was used to simulate benzene attenuation in the alluvial aquifer towards the Meuse River. The mean benzene degradation rate used in the model was quantified in situ along the groundwater flow path using compound-specific carbon isotope analysis (CSIA). The results of the solute transport simulations confirmed that benzene concentrations decreased almost five orders of magnitude 70 m downgradient the source. Simulated concentrations have been found to be below the detection limit in the zone adjacent to the river and consistent with the absence of benzene in downgradient piezometers located close to the river reported in groundwater sampling campaigns. In a transient model scenario including groundwater–surface water dynamics, benzene concentrations were observed to be inversely correlated to the river water levels, leading to the hypothesis that benzene dispersion is mainly controlled by natural attenuation.

Deposition, turnover and movement of persistent organic pollutants (POP) were investigated in the EU integrated project “AquaTerra”, which is among the first funded environmental projects within the 6th Framework Program by the European Commission. Project work integrates across various disciplines that range from biogeochemistry, environmental engineering, computer modelling and chemistry to socio-economic sciences. Field study areas are the river basins of the Ebro, the Meuse, the Elbe and the Danube as well as the 3-km2 French catchment of the Brévilles Spring. Within the first 2 years of the project more than 1700 samples of atmospherically deposited particles, sediments, and water have been collected in the above-mentioned systems. Results show clear spatial patterns of deposition of polyaromatic hydrocarbons (PAHs) with the highest rates in the Meuse Basin. For local inputs, in the Brévilles sandy aquifer, the contamination of the groundwater by the pesticides atrazine (AT) and deethylatrazine did not decrease even 5 years after their agricultural inputs were stopped. On the other hand, herbicides such as mecroprop (MCPP), and PAHs, were at least partially degraded microbiologically in laboratory studies with soils and aquifer material from selected sites. For sediment transport of contaminants, new flood sampling techniques revealed highest deposition rates of β-hexachlorocyclohexane (β−HCH) in river sediments at hotspot areas on the Mulde River in the Bitterfeld region (Elbe Basin, Germany). These selected preliminary results of AquaTerra help to improve fundamental understanding of persistent organic pollutants (POP) in the environment.

International audience; A pipeline transporting crude-oil broke in a nature reserve in 2009 and spilled 5100 m(3) of oil that partly reached the aquifer and formed progressively a floating oil lens. Groundwater monitoring started immediately after the spill and crude-oil recovery by dual pump-and-skim technology was operated after oil lens formation. This study aimed at documenting the implementation of redox-specific natural attenuation processes in the saturated zone and at assessing whether dissolved compounds were degraded. Seven targeted water sampling campaigns were done during four years in addition to a routine monitoring of hydrocarbon concentrations. Liquid oil reached the aquifer within 2.5 months, and anaerobic processes, from denitrification to reduction of sulfate, were observable after 8 months. Methanogenesis appeared on site after 28 months. Stable carbon isotope analyses after 16 months showed maximum shifts in delta C-13 of +4.9 +/- 0.22 parts per thousand for toluene, +2.4 +/- 0.19 parts per thousand for benzene and +0.9 +/- 0.51 parts per thousand for ethylbenzene, suggesting anaerobic degradation of these compounds in the source zone. Estimations of fluxes of inorganic carbon produced by biodegradation revealed that, in average, 60% of inorganic carbon production was attributable to sulfate reduction. This percentage tended to decrease with time while the production of carbon attributable to methanogenesis was increasing. Within the investigation time frame, mass balance estimations showed that biodegradation is a more efficient process for control of dissolved concentrations compared to pumping and filtration on an activated charcoal filter. (C) 2015 Elsevier B.V. All rights reserved.

Cette revue expose l’état actuel des connaissances concernant les biocénoses microbiennes présentes dans les aquifères oligotrophes. L’impact d’une contamination sur les biocénoses est discuté, ainsi que le potentiel que représentent les communautés ou un organisme spécifique, en tant qu’indicateur de qualité des eaux souterraines. En dernier lieu les méthodes à disposition en microbiologie sont examinées. Les aquifères sont hétérogènes à de nombreuses échelles et sont structurés en une grande variété d’habitats. Les espaces vides sont très souvent de petite taille. De ce fait, les biocénoses sont composées de manière prédominante par des microorganismes et parfois quelques micro-invertébrés. Les espaces plus larges, notamment les cavités karstiques, sont peuplés de macro-organismes également. En l’absence de toute forme d’énergie lumineuse, les biocénoses dépendent de sources d’énergie chimiques, présentes en faible quantité dans les aquifères non contaminés. Les microorganismes développent ainsi de petites tailles, une densité de population faible et une activité réduite. La physiologie des organismes est adaptée à la survie en conditions oligotrophes. Les bactéries sont planctoniques ou attachées aux matériaux de l’aquifère, ce qui demande un échantillonnage à la fois de l’eau et du substrat. De nombreuses méthodes sont aujourd’hui disponibles pour le comptage, l’identifi-cation et la caractérisation de la diversité, ainsi que la mesure des activités des organismes des aquifères. Comme la grande majorité des bactéries est viable mais non cultivable, les techniques de cultures actuelles ne donnent qu’une image incomplète des communautés, alors que les méthodes moléculaires développées récemment offrent la possibilité d’obtenir un profil de la communauté plus complet. The current knowledge of microbial biocenoses (communities) in pristine aquifers is presented in a review, which also discusses their relevance for questions of groundwater protection. Aquifers are heterogeneous on all scales and structured in a variety of habitats. The void spaces in many aquifers are small. The biocenoses are thus predominantly composed of microorganisms and, often, microinvertebrates. Larger voids and macroorganisms occur in karst cavities. Due to the absence of light, the biocenoses depend on chemical energy resources, which are, however, scarce in non-contaminated groundwater. The microorganisms thus show small cell sizes, low population densities and reduced activity; they developed specific strategies to survive oligotrophic conditions. The review also discusses the impact of contamination on the biocenoses, and the potential use of the biocenoses or specific organisms as indicators for groundwater quality, and the limits of this approach. Bacteria are either planktonic or attached to aquifer material, which requires both fluid and solid phase sampling. Most groundwater bacteria are viable but non-culturable. Consequently, cultivation techniques give an incomplete picture of the biocenoses, while methods from molecular microbiology provide genetic fingerprints of the entire community. Different analytical methods are available to count microorganisms, identify species, characterise microbial diversity, and measure activity. Se presenta una reseña crítica del conocimiento actual de biocenosis microbiana (comunidades) en acuíferos prístinos la cual también discute su relevancia en términos de protección de aguas subterráneas. Los acuíferos son heterogéneos en todas las escalas y estructurados en una variedad de habitats. Los espacios vacíos en muchos acuíferos son pequeños. La biocenosis está por lo tanto compuesta predominantemente por microorganismos y, frecuentemente, microinvertebrados. Espacios más grandes y macroorganismos ocurren en cavidades kársticas. Debido a la ausencia de luz la biocenosis depende de recursos energéticos químicos los cuales, sin embargo, son escasos en agua subterránea no contaminada. Los microorganismos muestran entonces tamaños de células pequeñas, bajas densidades de población y actividad reducida por lo que desarrollan estrategias específicas para sobrevivir en condiciones oligotróficas. Esta reseña crítica también discute el impacto de la contaminación en la biocenosis y el uso potencial de la biocenosis o de organismos específicos como indicadores de la calidad del agua subterránea, así como los límites de este enfoque. Las bacterias se encuentran ya sea en forma planctónica o ligadas al material acuífero lo cual requiere muestreo de la fase sólida y la fase fluida. La mayoría de bacterias de agua subterránea son viables pero no cultivables. Por lo tanto, las técnicas de cultivo aportan un cuadro incompleto de la biocenosis mientras que los métodos de microbiología molecular aportan señales genéticas de toda la comunidad. Existen diferentes métodos analíticos para contar microorganismos, identificar especies, caracterizar diversidad microbiana, y medir actividad.

Geochemical heterogeneities may cause spatial variations in virus inactivation rates resulting from interactions with minerals leading to differences in natural disinfection capacity within an aquifer. Column studies investigating the interaction of the bacteriophage H40/1 with natural sands sampled from the Kappelen test site (Kappelen), Bern, Switzerland indicated that inactivation rates are higher for adsorbed bacteriophages than for those suspended in groundwater. Moreover, breakthrough curves obtained from field-based tracer tests at Kappelen indicated that the adsorbed H40/1 is inactivated in-situ at comparable rates. Statistical analyses of mineralogical data failed to demonstrate significant spatial variations in aquifer composition either across the site or with depth. In contrast hydrochemical analyses of groundwater samples collected at Kappelen demonstrated that iron-reducing groundwater occurs below aerobic waters. Tracer breakthrough curves indicate that H40/1 survival is not affected by variable redox conditions. Investigation results suggest that spatial geochemical variability does not significantly affect H40/1s inactivation rate at Kappelen.

The influence of rivers on the groundwater quality in alluvial aquifers can be twofold: direct and indirect. Rivers can have a direct influence via recharge and an indirect one by controlling the distribution of fine-grained, organic-carbon rich flood deposits that induce reducing conditions. These direct and indirect influences were quantified for a large alluvial aquifer on the Swiss Plateau (50km(2)) in interaction with an Alpine river using nitrate as an example. The hydrochemistry and stable isotope composition of water were characterized using a network of 115 piezometers and pumping stations covering the entire aquifer. Aquifer properties, land use and recharge zones were evaluated as well. This information provided detailed insight into the factors that control the spatial variability of groundwater quality. Three main factors were identified: (1) diffuse agricultural pollution sources; (2) dilution processes resulting from river water infiltrations, revealed by the δ(18)OH2O and δ(2)HH2O contents of groundwater; and (3) denitrification processes, controlled by the spatial variability of flood deposits governed by fluvial depositional processes. It was possible to quantify the dependence of the nitrate concentration on these three factors at any sampling point of the aquifer using an end-member mixing model, where the average nitrate concentration in recharge from the agricultural area was evaluated at 52mg/L, and the nitrate concentration of infiltrating river at approximately 6mg/L. The study shows the importance of considering the indirect and direct impacts of rivers on alluvial aquifers and provides a methodological framework to evaluate aquifer scale water quality patterns.

This study presents a stepwise concept to assess the in situ microbial mineralization of petroleum hydrocarbons (PHC) in aquifers. A new graphical method based on stable carbon isotope ratios (δ13C) was developed to verify the origin of dissolved inorganic carbon (DIC). The concept and the isotope method were applied to an aquifer in Studen, Switzerland, in which more than 34,000 liters of heating oil were accidentally released. Chemical analyses of ground water revealed that in this aquifer locally, anaerobic conditions prevailed, and that PHC mineralization was linked to the consumption of oxidants such as O2, NO2-, and SO42- and the production of reduced species such as Fe2+, Mn2+, HSS and CH4. However, alkalinity and DIC balances showed a quantitative disagreement in the link between oxidant consumption and DIC production, indicating that chemical data alone may not be a reliable assessment tool. δ13C ratios in DIC have been used before for bioremediation assessment, but results were reported to be negatively influenced by methanogenesis. Using the new graphical method to display δ13C data, it was possible to identify anomalies found in methanogenic monitoring wells. It could be shown that 88% of the DIC produced in the contaminated aquifer originated from microbial PHC mineralization. Thus, the new graphical method to display δ13C ratios appears to be a useful tool for the assessment of microbial hydrocarbon mineralization in a complex environment.

Engineered in situ bioremediation is an economically and ecologically sound technology for the clean-up of contaminated soils and aquifers. However, a successful bioremediation requires solid evidence for the detoxification of the contaminants, preferably proven by complete mineralization. This paper discusses a stepwise evaluation leading to the demonstration of successful engineered in situ bioremediation. Five major evaluation steps assess whether: (1) the contaminants can be mineralized by the indigenous microbial population (2) the mineralization rates can be increased (3) the remediation concept can be simulated under continuous flow conditions (4) the increase of mineralization rates can be achieved at the field site (scale-up), and (5) complete mineralization to harmless end products is achieved at the field site. For these evaluations, the applicability of four experimental approaches (field investigations, laboratory aquifer columns, microcosms and microbial cultures) and the relevance of various microbiological or chemical monitoring parameters are discussed. The evaluations are illustrated using a specific engineered in situ bioremediation of a diesel fuel-contaminated aquifer in Menziken, Switzerland. The case study demonstrates that microbiological and chemical monitoring parameters as well as field tracer studies and stable carbon isotopes should be combined for the unequivocal evaluation of engineered in situ bioremediation.

A field investigation of a TCE plume in a surficial sand aquifer shows that groundwater-surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of microg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of microg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water-air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone.

Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26 per thousand), which is consistent with field observations. At most sampling points, the delta(13)C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a (13)C enrichment of up to 2.4 per thousand was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with (12)C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the delta(13)C values varied substantially from -24.3 per thousand to -33.6 per thousand. Comparison of the delta(13)C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in delta(13)C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network.

In-situ bioremediation of mineral oil contaminated soils and aquifers can be a powerful technique. However, due to the heterogeneity and the complex chemical and biological characteristics of the subsurface, the efficiency of this technique is difficult to assess and the fate of the hydrocarbons often remains unknown. Therefore, in-situ bioremediation should (i) include monitoring concepts that allow a reliable quantification of the degradation rates of mineral oil, and (ii) be accompanied by studies in defined laboratory systems (e.g. aquifer columns and microbial cultures) to simulate specific processes and to determine the fate of selected components of mineral oil.