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A key aspect of protecting aquatic ecosystems from agricultural nitrogen (N) is to locate (i) farmlands where nitrate leaches from the bottom of the root zone and (ii) denitrifying zones in the aquifers where nitrate is removed before entering the surface water (N-retention). N-retention affects the choice of field mitigation measures to reduce delivered N to surface water. Farmland parcels associated with high N-retention gives the lowest impact of the targeted field measures and vice versa. In Denmark, a targeted N-regulation approach is currently implemented on small catchment scale (approx. 15 km2). Although this regulatory scale is much more detailed than what has been used previously, it is still so large that regulation for most individual fields will be either over- or under-regulated due to large spatial variation in the N-retention. The potential cost reduction for farmers is of up to 20–30% from detailed retention mapping at the field scale compared to the current small catchment scale. In this study, we present a mapping framework (N-Map) for differentiating farmland according to their N-retention, which can be used for improving the effectiveness of targeted N-regulation. The framework currently only includes N-retention in the groundwater. The framework benefits from the incorporation of innovative geophysics in hydrogeological and geochemical mapping and modelling. To capture and describe relevant uncertainties a large number of equally probable realizations are created through Multiple Point Statistical (MPS) methods. This allows relevant descriptions of uncertainties of parts of the model structure and includes other relevant uncertainty measures that affects the obtained N-retention. The output is data-driven high-resolution groundwater N-retention maps, to be used by the individual farmers to manage their cropping systems due to the given regulatory boundary conditions. The detailed mapping allows farmers to use this information in the farm planning in order to optimize the use of field measures to reduce delivered agricultural N to the surface water and thereby lower the costs of the field measures. From farmer interviews, however, it is clear that not all farms will have an economic gain from the detailed mapping as the mapping costs will exceed the potential economic gains for the farmers. The costs of N-Map is here estimated to 5–7 €/ha/year plus implementation costs at the farm. At the society level, the N-retention maps allow authorities to point out opportunities for a more targeted implementation of field measures to efficiently reduce the delivered N-load to surface waters.

Salinity levels above the drinking water standard (>250 mg/l Cl–) are observed at shallow depth in a Maastrichtian chalk aquifer on the island of Falster, south-eastern Denmark. To understand the source of the salt, 63 samples from 12 individual, 1 m, screened intervals between 14 and 26 m b.s. were collected from 1 May to 4 June 2018. The samples were collected during a tracer test to estimate the dual porosity properties of the chalk and were analysed for a wide range of elements. Furthermore, samples from the Baltic Sea and from deeper saline aquifers in the area (40 and 85 m b.s.) were analysed for comparison. The geochemical data were analysed using an unsupervised machine-learning algorithm, self-organising maps, to fingerprint water sources. The water composition in the screened intervals at various stratigraphic levels has specific geochemical fingerprints that are maintained for the first days of pumping and are distinct amongst the different levels. This suggests an evolution in water composition because of reaction with the chalk. Water composition is distinct from both seawater from the nearby Baltic Sea and salty water from deeper levels of the reservoir. Thus, neither up-coning of salty water nor intrusion of seawater caused the elevated salinity levels in the area. The slightly saline composition of groundwater in the shallow aquifer (14–26 m b.s.) is more likely because of incomplete refreshing of the salty connate water in the chalk during the Pleistocene and Holocene. Furthermore, the geochemical fingerprint of salty water from the deeper aquifer at 40 m was similar to water from the Baltic Sea, suggesting a Baltic Sea source for salt in the aquifer at 40 m b.s., c. 100 m from the coast. Statistical analysis based on self-organising maps is an effective tool for interpreting a large number of variables to understand the compositional variation in an aquifer and a useful alternative to linear dimensionality-reduction methods such as principal component analysis. The approach using the multi-element analysis combined with the analysis of self-organising maps may be useful in future studies of groundwater quality.

The large natural gas storage facility at Stenlille, Denmark, has been monitored to investigate the effect of pumping large amounts of gas into the subsurface. Here, we present a new dataset of microseismicity at Stenlille since 2018. We compare these data with methane in groundwater, which has been monitored since gas storage was established in 1989. Further, we conducted a controlled 172 day microcosm experiment of methane oxidation on an isolated microbial community under both aerobic and anaerobic conditions. For this experiment, water was filtered from a well at Stenlille with elevated levels of thermogenic methane and ethane. No microseismic activity was detected in the gas storage area above an estimated detection level of ML 0.0 for the established network. The long-term monitoring for methane in groundwater has still only detected one leak, in 1995, related to a technical problem during injection. The microcosm experiment revealed that oxidation of methane occurred only under aerobic conditions during the experiment, as compared to anaerobic conditions, even though the filtered water was anoxic

Arsenic (As) is highly toxic and over 100 million people living on the floodplains of Asia are exposed to excessive groundwater As. A very large spatial variability over small distances has been observed in the groundwater As concentrations. Advances in the prediction of the As distribution in aquifers would support drinking water management. The application of remote sensing of geomorphic paleo river features combined with geological, geophysical and archeological data and available groundwater As measurements may be used to predict groundwater As levels in rural areas, as shown by the example from the Red River delta, Vietnam. Groundwater in sediments deposited in the marine environment is low in As, probably due to the precipitation of As in sulfide minerals under anoxic conditions. Groundwater As levels in freshwater alluvial deposits in undisturbed floodplain areas are slightly increased and the highest As concentrations are associated with meander belts. The meander belts remain clearly visible in remote sensing and may well reflect the youngest preserved alluvial sediments. High As levels in the meander belt aquifers are probably related to the availability of highly reactive organic matter and consequent reduction of iron oxyhydroxides and As release. Furthermore, given similar hydrogeological conditions, the extent of flushing of As from the youngest alluvial sands is limited compared to the older Pleistocene sands. Even within abandoned meander belts a high spatial variability of As concentrations was observed. The younger channel belts (

When groundwater-based drinking water supply becomes contaminated, the timing and source of contamination are obvious questions. However, contaminants often have diffuse sources and different contaminants may have different sources even in a single groundwater well, making these questions complicated to answer. Age dating of groundwater has been used to reconstruct contaminant travel times to wells; however, critics have highlighted that groundwater flow is often complex with mixing of groundwater of different ages. In drinking water wells, where water is typically abstracted from a large depth interval, such mixing is even more problematic. We present a way to overcome some of the obstacles in identifying the source and age of contaminants in drinking water wells by combining depth-specific sampling with age tracer modeling, particle tracking simulations, geological characterization, and contaminant properties. This multitool approach was applied to a drinking water well, where bentazon and dichlorprop contamination was found to have different pollutant sources and release histories, even though both pesticides can be associated with the same land use. Bentazon was derived from recent application to a golf course, while dichlorprop was derived from agricultural use more than 30 years ago. The advantages, limitations, and pitfalls of the proposed course of action are then further discussed.

The spatial and temporal variability of denitrification makes it challenging to integrate conceptual, process-based understandings of nitrate transport and retention into numerical modeling at the catchment scale, although it is critical for the realism and predictive power of the model. In this study, we propose a novel approach where the conceptual understandings of the spatial structure of denitrification zones and the corresponding representative denitrification rates are transformed into a form that can be integrated into a multi-point statistical simulation framework. This is done by constructing a denitrification training image (TI) coupled to a geophysically based TI of the hydrogeological structure. The field observations and laboratory analyses of denitrification rates and the chemistry of water and sediment revealed that the study catchment’s subsurface can be characterized by three zones: (1) the oxic zone with no nitrate reduction; (2) the slow-denitrification zone (mean of ln-transformed rate = −1.19 ± 0.52 mg N L-1yr-1); and (3) the high-denitrification zone (mean of ln-transformed rate = 3.86 ± 1.96 mg N L-1yr-1). The underlying controls on the spatial distribution of these zones and the representativeness of denitrification rates were investigated. Then, a TI illustrating the subsurface structure of the denitrification zone was constructed by synthesizing the results of these geochemical interpretations and the hydrogeology TI.

Diffuse pollution of nitrate from agricultural fields is a critical environmental problem around the world. Sources and sinks of nitrate are heterogeneously distributed over various spatial scales, and the connectivity and transport pathways between them also change at different temporal scales. Therefore, understanding the impact of these variabilities in nitrate transport to the aquatic environment is fundamental for a correct numerical modelling of nitrate transport within a catchment. This study, hence, investigated controls on the spatiotemporal variability of nitrate in a glacial landscape and upscaled it to catchment scale by synthesizing geological, hydrogeochemical, and geophysical information. We found that different parts of the sedimentary succession define the locations of nitrate sinks in this catchment. Denitrification mainly may occur mainly around small patches of postglacial sediments on the outwash plain, which is the youngest formation covering the top layer of the catchment. In contrast, in older geological elements, which constitute the hill and the layers below the outwash plain, oxic, nitrate-containing groundwater was found, probably because of depletion of reduced compounds over the long exposure time. We also found that the boundary between these two formations may govern the seasonal shift of this oxic groundwater's connectivity to the stream consequently nitrate export from the catchment. This conceptual understanding of nitrate transport and sinks then was transformed into a 3D hydrogeochemistry model based on a high-resolution resistivity model of the catchment. We propose that such a basic understanding of how a catchment hydrogeochemically operates should be the first step toward setting up a catchment scale hydrological model with reactive N transport.

Hyporheic sediments are influenced by physical, biological, and chemical processes due to the interactions with river water and has been shown to play an important role in the environmental fate of pesticides. Therefore, this study evaluated the bacterial degradation potential of MCPA, metolachlor and propiconazole in hyporheic sediments sampled along a 20 km long stretch of an agriculturally impacted river dominated primarily by water losing conditions. Water physicochemical parameters in the river and nearby groundwater wells were assessed along with pesticide sorption to sediments and bacterial community composition. Degradation and mineralisation batch experiments were set up from six locations (five water losing, one water gaining) using environmentally relevant concentrations of pesticides (10 μg kg

Machile-Zambezi Basin, South-Western Zambia hosts high salinity groundwater which threatens water security for rural inhabitants. This study investigates the hydrological mechanism that led to high salinity and the geochemical evolution of the groundwater system. The Machile-Zambezi Basin is part of the wider Kalahari Basin which underwent major palaeo-environmental climatic, tectonic and sedimentology dynamics which must have impacted the groundwater salinity. The study examines the groundwater level, hydrochemistry, environmental isotopes (18O/16O, 2H/1H, 3H/3He, 14C/13C). In addition, the sediment cation exchange capacity (CEC) and pore-water chemistry on intact core material were measured. The groundwater chemistry evolved from fresh Ca(Na)HCO3 to saline Na(Ca, Mg)SO4 due to dissolution of salts and not evaporation as indicated by stable isotopes. The saline groundwater is old with 14C ages estimates of more than 1000 years old and stagnant. Geochemical modelling using PHREEQC suggests that ionic exchange due to release of cations from dissolving salts and sulphate reduction were also important processes in this system. High groundwater salinity is therefore associated with Pre-Holocene environmental changes and is restricted to a stagnant saline zone. It will therefore remain unflushed as long as current climatic conditions remain.

The relation between arsenic groundwater concentrations and hydrogeological processes was investigated in the proximal part of the Red River delta, Vietnam, west of the depression cone formed by the exploitation of groundwater in Hanoi. Flow paths in the Quaternary aquifers were modeled based on previously interpreted geological structure and hydrogeological data gathered during field work in 2014-2017. Sedimentary structures and simulated flow patterns were compared with the spatial distribution of the groundwater arsenic concentration. The regression of the sea in the area started 4 ka BP in the Holocene. The low tectonic subsidence rate of the Red River delta led to intensive erosion and replacement of fine grained sediments of the sea level high stand by sandy channel belts, resulting in hydraulic connections between the Pleistocene and Holocene aquifers. The Pleistocene aquifer is recharged by both regional flow paths and naturally occurring vertical recharge through Holocene sand and clay layers. Young groundwater (40 a) in the shallow Holocene aquifer generally discharges to surface water bodies. The shallow flow system is also seasonally recharged with surface water, as indicated by δ

The adsorption of As(III) onto reduced sediment from Holocene aquifers in the Red River floodplain, Vietnam, was studied in batch experiments under strict anoxic conditions using sandy sediments from four different sites with a sediment burial age between 600 and 3500 years. Sediments containing the highest content of Fe-oxide showed the highest As(III) adsorption capacity. Removal of the Fe-oxides from the sediment by reductive dissolution significantly reduced the As(III) adsorption capacity of the residual sediment. Normalizing the adsorption of As(III) to the amount of Fe-oxides in the untreated sediments resulted in almost identical adsorption isotherms. We therefore conclude that Fe-oxides are the main adsorbents for As(III) in these reduced aquifer sediments. However, the properties of the sedimentary Fe-oxides are different from those of synthetic Fe-oxides since we found that adsorbed As(III) is not displaced by phosphate and neither is the adsorption of As(III) influenced by changes in pH between 6.2 and 7.5. In the absence of competition for surface sites, As(III) adsorption onto aquifer sediment can be described by a Langmuir isotherm normalized to the amount of Fe-oxides present in the sediment. The finding that the As(III) adsorption capacity depends on the Fe-oxide content of the sediment implies that the As(III) sorption capacity will decrease over time because of reductive dissolution of Fe-oxides, which again is coupled to the burial age of the sediment. In consequence, reactive transport models need to include how aquifer properties, like sorption capacity, change as a function of the extent of chemical reaction.

Understanding thefactors that control As concentrations in groundwater is vital for supplying safe groundwaterin regions with As-polluted aquifers. Despite much research, mainly addressing Holocene aquifers hosting young (12,000 yrs) groundwatersare not yet fully understood and so are assessed here through an evaluation of the redox properties of the system in a type locality, the PoPlain (Italy).Analyses of redox-sensitive species and major ions on 22 groundwater samples from the Pleistocene arsenic-affected aquifer in the Po Plain shows that groundwater concentrations of As are controlled by the simultaneous operation of several terminal electron accepters. Organic matter, present as peat, is abundant in the aquifer, allowing groundwater to reach a quasi-steady-state of highly reducing conditions close to thermodynamic equilibrium. In this system, simultaneous reduction of Fe-oxide and sulfate results in low concentrations of As (median 7 μg/L) whereas As reaches higher concentrations (median of 82 μg/L) during simultaneous methanogenesis and Fe-reduction. The position of well-screens is an additional controlling factor on groundwater As: short screens that overlap confining aquitards generate higher As concentrations than long screens placed away from them. A conceptual model for groundwater As, applicable worldwidein other Pleistocene aquifers with reducible Fe-oxides andabundant organic matter is proposed: As may have two concentration peaks, the first after prolonged Fe-oxide reduction and until sulfate reduction takes place, the second during simultaneous Fe-reduction and methanogenesis.

Water-sediment interactions were investigated in arsenic contaminated Holocene aquifers of the Red River floodplain, Vietnam, in order to elucidate the origin of the spatial variability in the groundwater arsenic concentration. The investigated aquifers are spread over an 8 × 13 km field area with sediments that varied in burial age from

A multi-species, multi-stable-isotope approach (δ15NNO3, δ18ONO3, δ34SSO4, δ18OSO4, δ18OH2O and δ2HH2O) was used together with environmental tracers (Ar, Ne, CFC-11 and CFC-12) and geochemical modelling to characterize sources and processes controlling concentrations of NO3− and SO42- in groundwater of the carbonate aquifer Gliwice (southern Poland). The study area represents a strongly transformed environment with a range of human activities i.a. Agriculture, urbanization and industry. The δ15NNO3 and δ18ONO3 indicated that most samples contained NO3− of mixed sources: artificial fertilizers, municipal and industrial sewage, while very good correlation between NO3− and CFC-12 suggested that nitrate originated primarily from residential and industrial sewage. Conversely, isotopic composition of sulphate in groundwater suggested agriculture as well as oxidation of sulphides as dominant. The conclusion was supported by the comparison of CFCs and sulphate concentrations which revealed no relevant correlation. Geochemical modelling confirmed the presence of sulphate reduction in areas where isotopic analyses were not possible due to undetectable sulphate. Thus, the integrated application of stable isotopes, environmental tracers, groundwater chemistry and geochemical modelling shows a complex origin of groundwater pollution in the study area as well as variety of geochemical processes controlling chemistry of groundwater in a triple-porosity aquifer influenced by different types of human activity.

Adsorption of As(III) to aquifer sediments from the Red River floodplain, Vietnam, has been studied with the aim of identifying controlling parameters for the adsorption. The adsorption capacity differs between similar sediments, indicating that it is not related to bulk components of the sediment but rather that certain properties of the sediments are important for the adsorption. Normalizing the adsorption of As(III) to the content of Fe-oxides in the sediments results in almost identical adsorption isotherms, indicating that Fe-oxides are the main adsorbents for As(III) in these three reduced aquifer sediments. This is further strengthened by adsorption experiments carried out with sediments leached for Fe-oxides, as this resulted in reduced adsorption capacity and despite the difference in adsorption capacity of the untreated sediments, the adsorption capacity became identical after Fe-oxide leaching. The importance of Fe-oxides for As(III) adsorption to reduced aquifer sediments has implications for the mobility of As(III) in the groundwater aquifers, as it will vary spatially and also over time, as the Fe-oxides in the sediment are reduced.

Many agricultural soils are tile drained in order to lower water tables and improve crop production, but tile drains have a large impact on water flows and nutrient transport. The objectives of the study were to assess modelling requirements for describing shallow groundwater and tile drainage dynamics and to evaluate how tile drains affect groundwater flow across the redox interface, where nitrate reduction in the subsurface occurs. The study was conducted on a 33-hectare tile drained field within a Weichsel till area in Fensholt catchment, Denmark. The study consisted of 2.5 years high-frequency monitoring and numerical modelling using a variably-saturated 3D hydrological model (FEFLOW) with a detailed representation of the tile drain network. Field data showed extremely rapid increases, up to 1 m per day, in the groundwater heads when the autumn water surplus starts. Drain discharge was found to follow the dynamics in heads. High-frequency monitoring (at least once per day) is therefore necessary in order to capture the dynamics in shallow groundwater and tile discharge. The dynamics showed simultaneous rapid increase in groundwater heads down to a depth of 22 m, illustrating the key importance of deeper geology in understanding the hydrological processes in this area. The temporal dynamics in head and drain discharge were successfully captured by the hydrological model and the steepness of the retention curve was found to be important for this. The calibrated model was successfully tested against discharge in the stream draining a larger area. The model results showed, that tile drains affect the water flow in the area and significantly decrease the downward fluxes across the redox interface, located on average at 3.6 m depth. Tile drains therefore have a large effect on the amount of nitrate reduction in the subsurface and on the nitrate fluxes to receiving surface waters.

Combined geological, hydrogeological, and geochemical controls on the arsenic concentration of contaminated aquifers in SE Asia were explored by two‐dimensional (2‐D) reactive transport modeling of data sets from Bangladesh, Cambodia, and Vietnam. For each site, the field data are summarized and used to create a conceptual 2‐D reactive transport model that elucidates characteristic features influencing the groundwater arsenic concentration. Comparison of models for Bangladesh and Vietnam indicates that fine‐grained layers overlying young sandy aquifers generate shallow high arsenic groundwater because low vertical groundwater velocities allow sufficient time for kinetic As release from the sediment. The low vertical groundwater velocity below major river channels, predicted by the model, also creates long groundwater residence times, leading to high arsenic groundwater. Young aquifer sediments release more arsenic than older sediments, and alternating young and older sediments create complex patterns of high and low arsenic groundwater. Over time, floodplain basins will subside, and river channels migrate, causing sedimentation and erosion on the floodplain while creating local environments with evolving hydrogeology and groundwater geochemistry. We have developed a three‐step model for the evolution of the Red River floodplain with sedimentation and shifting channels over the last 6000 years. The results show comparable timescales between the dynamics of arsenic release and of river migration, causing complex groundwater As distributions, comprising geochemical palinopsia of long vanished rivers., Key Points Characteristic examples of high As groundwater can be modeled by 2‐D reactive transport models using PHAST with a common geochemical modelThe 2‐D reactive transport models may include effects of geological development with shifting channels, erosion, and depositionThe observed variability in the As distribution is a function of the sedimentological history, hydrogeology, and age‐dependent release of As

Cost-efficient targeted nitrogen (N) regulation of agriculture with low impact on the environment is the new N regulation paradigm. It requires detailed knowledge on the geological and geochemical conditions of the subsurface that is crucial for assessing the nitrate flowpaths and reduction processes. An integral part of this is analysis of the subsurface redox structures to determine the locations of nitrate reduction. This knowledge has so far not been easy to access because of lacking technology. Here we present a new concept consisting of integration and interpretation of data from the geophysical towed transient electromagnetic method, borehole information on lithology, sediment colour descriptions, geochemistry and groundwater chemistry. The concept is demonstrated in three small first-order hydrological catchments. National GIS screening analyses show that the new concept is highly needed in large parts of Denmark where the redox structures are complicated e.g. in marine landscape types and in glacial moraine landscapes but less needed in areas dominated by homogeneous meltwater plains. Providing subsurface knowledge for locally targeted N regulation of agriculture is paramount in many developed countries with intensive agriculture to lower the environmental impact, and it could also be critical in developing countries to support sustainable economic and environmental development.

Groundwater As concentrations >WHO limit (10 μg/L) are frequently found in the Po Plain (N. Italy). Although several hypotheses on As mobilization exist (i.e., reductive dissolution driven by peat degradation), the mechanisms of As release and subsequent attenuation acting in the multilayer aquifer in the Po Plain were poorly understood.The present work aims at implementing a reactive transport modeling of the aquifer system in Cremona, affected by As

The arsenic content in groundwater of the Red River floodplain decreases with the burial age of the aquifer sediment over a 6000 year period. This decrease is caused by diminishing reactivities of both sedimentary organic carbon, Fe-oxides as well as CaCO3. Here we present a 1-D reactive transport model developed in PHREEQC-3 that quantifies the resulting changes in groundwater bulk chemistry as well as arsenic content over the last six millennia.

Nitrogen (N) leaching caused by agricultural activities is one of the major threats to the aquatic ecosystems and public health. Moving from the agricultural soils through the subsurface and reemerging to the surface water, N undergoes various biogeochemical reactions along pathways in the subsurface, which occur heterogeneously in space and time. Thus to improve our understanding on the fate and distribution of N in the aquatic environment, detailed knowledge about the subsurface hydrogeological and biogeochemical conditions, especially the redox conditions, are essential. In this study, 3D information of the redox conditions termed the redox architecture was investigated in two Danish catchments with intensive agriculture underlain by glacial deposits. Towed transient electromagnetic (tTEM) resistivity was interpreted which reveals the subsurface geological structures at a few hectare scale. These geophysical data were integrated with sediment and water chemistry for the redox architecture interpretations. The top soils of both catchments are characterized as clay-till, but the tTEM showed that the subsurface hydrogeological structures are distinctively different. We identified three types of redox architectures in the studied catchments: 1) a planar redox architecture with a single redox interface; 2) a geological-window redox architecture with local complexity; and 3) a glaciotectonic-thrusted redox architecture with high complexity. The baseflow N load at the catchment outlets reflect the contributions of N via oxic pathways through the complex redox architectures of the subsurface. We conclude that in some landscapes, the redox architecture cannot be simplified as a single interface that roughly follows the terrain; hence, thorough investigations of the structural heterogeneity of the local redox architectures will be necessary to improve simulations of N evolution along pathways and quantifications of N attenuation under various mitigation scenarios.

To assess the contribution of reactive nitrogen from groundwater to surface waters, we need more knowledge on how reactive nitrogen behaves in the glacial till systems underlying many agricultural fields. Groundwater sampled from suction cups and piezometers placed in the glacial till underlying a winter wheat field shows the nitrate concentration in water leaching to deeper than 2 m below ground surface (mbg) is ~ 60 mg L(−1). Within 5 mbg, all of the nitrate is removed and this appears to take place within a redox zone rather than at a sharp redox front. Ammonium released from the till is negligible. A 2D dataset reveals that the depth to the redox zone undulates between 3 and 5 mbg, perhaps a result of local variations in infiltration. It appears that the nitrate is generally reduced by the oxidation of pyrite and locally by organic matter in lenses within the till. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s13280-019-01228-4) contains supplementary material, which is available to authorized users.

Bornholm is situated south of Sweden, in the Sorgenfrei–Tornquist Zone (Fig. 1). The Precambrian basement on northern and eastern Bornholm consists of different types of granitic and gneissic rocks with pegmatites, aplites and dolerite dykes (Callisen 1934). The age of the granite and gneiss is c. 1455 Ma (Waight et al. 2012).

A geochemical numerical modeling study was conducted to constrain processes occurring in field and laboratory experiments, simulating CO 2 leakage from geological storage on shallow potable aquifers. A leak was previously physically simulated in a shallow potable aquifer at Vrogum plantation, Western Denmark by injection of 1600 kg of gas phase CO 2 over 72 days. Here, a 1-dimensional reactive transport model was constructed based on field and laboratory results and subsequently used to explore the contributions of various geochemical processes to explain observed results from the carbonate free system. Finite gibbsite derived Al 3+ driven cation exchange is able to explain the majority of water chemistry change observed at Vrogum including: a pulse like effect showing a fast peak and return toward background levels for alkalinity and dissolved ion concentrations; and increasing and persistent acidification via buffering exhaustion. Model processes were supported further by simulation of a batch experiment conducted on the Vrogum glacial sand, employing the same processes and sediment parameters. The fitted reactive transport model was subsequently used to extend predictions and explore various scenarios. Extended predictions suggest the pulse of elevated ions travels with advective flow succeeded by a zone of increasing acidification. Model runs at higher P CO2 (implying greater depths) suggest amplification of effects, i.e., greater peaks and more rapid and severe acidification. Calcite limits acidification, however, induces additional Ca driven ion exchange giving rise to more significant chemistry change. Although a site specific model, results have significant implications for risks posed to water resources from CCS leakage and implementation of MMV programs.

Several soil remediation techniques for As, Cu and Cr contaminated soil utilize adsorption of contaminants to ferrihydrite as the removal mechanism, even though ferrihydrite will transform to secondary iron oxides and part of the sorption capacity will be lost. Transformation of ferrihydrite following 4 yr of in situ burial at a contaminated site was examined in samples of impure (Si-bearing) ferrihydrite in soil heavily polluted with As, Cr and Cu. The samples are so-called iron water treatment residues (Fe-WTR) precipitated from anoxic groundwater during aeration. The extent of transformation of ferrihydrites in the field was evaluated in the lab through experiments where the kinetics of iron and contaminant release was studied in a pH 3 ascorbic acid solution. Compared to fresh controls the aged samples had scavenged significant amounts of contaminants (up to 9.2 mmolAs/molFe and 1.5 mmolCu/molFe) and the reactivity had decreased by one order of magnitude, indicating partial transformation of ferrihydrite to more crystalline iron phases. Iron crystallinity increased during the 4 yr of aging with XRD suggesting goethite, α-FeO(OH), to be the most prominent transformation products. The study clarifies the fate of ferrihydrite and associated contaminants during burial enabling an improvement of the methods for amending contaminated soil with Fe-WTR.

Establishment of electrochemical zones for remediation of dissolved chlorinated solvents in natural settings was studied. An undivided 1D-experimental column set-up was designed for the assessment of the influence of site-extracted contaminated groundwater flowing through a sandy aquifer material, on the execution of laboratory testing. A three-electrode system composed of palladium coated pure iron cathodes and a cast iron anode was operated at 12 mA under varying flow rates. The natural settings added complexity through a diverse groundwater chemistry and resistance in the sand. In addition, significant precipitation of iron released through anode corrosion was observed. Nevertheless, the complex system was successfully modelled with a simple geochemical model using PHREEQC. A ranking of the significances of system parameters on the laboratory execution of electrochemical remediation in natural settings was proposed: Geological properties > anode corrosion > site-extracted contaminated groundwater > the carbonate system > sulphate > hydrology > less significant unidentified parameters. This study provides insight in actual challenges that need to be overcome for in situ electrochemical remediation.

Density functional theory-based molecular dynamics calculations of condensed phase systems often benefit from the use of hybrid functionals. However, their use is computationally very demanding and severely limits the system size and time scale that can be simulated. Several methods have been introduced to accelerate hybrid functional molecular dynamics including Schwarz screening and the auxiliary density matrix method (ADMM). Here we present a simple screening scheme that can be applied in addition to these methods. It works by examining Hartree-Fock exchange (HFX) integrals and subsequently excluding those that contribute very little to any nuclear force component. The resultant force error is corrected by a history-dependent extrapolation scheme. We find that for systems where the calculation of HFX forces is a major bottleneck, a large fraction of the integrals can be neglected without introducing significant errors in the nuclear forces. For instance, for a 2 × 2 × 2 unit cell of CoO, 92% of the HFX integrals that have passed Schwarz screening within the ADMM approach can be neglected leading to a performance gain of a factor of 3 at a negligible error in nuclear forces (≤5 × 10

article i nfo Contamination of groundwater by leaking CO2 is a potential risk of carbon sequestration. With the help of a field experiment in western Denmark, we investigate to what extent surface electrical resistivity tomography (ERT) can detect and image dissolved CO2 in a shallow aquifer. For this purpose, we injected CO2 at a depth of 5 and 10 m and monitored its migration using 320 electrodes on a 126 m × 25 m surface grid. A fully automated acquisition system continuously collected data and uploaded it into an online database. The large amount of data allows for time-series analysis using geostatistical techniques for noise estimation and data interpolation to compensate for intermittent instrument failure. We estimate a time-dependent noise level for each ERT configuration, taking data variation and measurement frequency into account. A baseline inversion reveals the geology at the site consisting of aeolian and glacial sands near the surface and marine sands below 10 m depth. 3-D time-lapse ERT inversions clearly image the dissolved CO2 plume with de- creased electrical resistivity values. We can image the geochemical changes induced by the dissolved CO2 until the end of the acquisition, 120 days after the injection start. During these 120 days, the CO2 migrates about 25 m in the expected groundwater flow direction. Water electrical conductivity (EC) sampling using small screens in 29 wells allows for very good verification of the ERT results. Water EC and ERT results generally agree very well, with the water sampling showing some fine-scale variations that cannot be resolved by the ERT. The ERT images have their strength in outlining the plume's shape in three dimensions and in being able to image the plume outside the well field. These results highlight the potential for imaging dissolved CO2 using non-intrusive surface electrical resistivity tomography.

A shallow aquifer CO2 contamination experiment was performed to investigate evolution of water chemistry and sediment alteration following leakage from geological storage by physically simulating a leak from a hypothetical storage site. In a carbonate-free aquifer, in western Denmark, a total of 1600 kg of gas phase CO2 was injected at 5 and 10 m depth over 72 days through four inclined injection wells into aeolian and glacial sands. Water chemistry was monitored for pH, EC, and dissolved element evolution through an extensive network of multilevel sampling points over 305 days. Sediment cores were taken pre and postinjection and analyzed to search for effects on mineralogy and sediment properties. Results showed the simulated leak to evolve in two distinct phases; an advective elevated ion pulse followed by increasing persistent acidification. Spatial and temporal differences in evolution of phases suggest separate chemical mechanisms and geochemical signatures. Dissolved element concentrations developed exhibiting four behaviors: (1) advective pulse (Ca, Mg, Na, Si, Ba, and Sr), (2) pH sensitive abundance dependent (Al and Zn), (3) decreasing (Mn and Fe), and (4) unaffected (K). Concentration behaviors were characterized by: (1) a maximal front moving with advective flow, (2) continual increase in close proximity to the injection plane, (3) removal from solution, and (4) no significant change. Only Al was observed to exceed WHO guidelines, however significantly so (10-fold excess). The data indicate that pH is controlled by equilibrium with gibbsite which is again coupled to cation exchange processes. Pre and postinjection sediment analysis indicated alteration of sediment composition and properties including depletion of reactive mineral species.

Aquifers on the Red River flood plain with burial ages ranging from 500 to 6000 years show, with increasing age, the following changes in solute concentrations; a decrease in arsenic, increase in Fe(II) and decreases in both pH, Ca and bicarbonate. These changes were interpreted in terms of a reaction network comprising the kinetics of organic carbon degradation, the reduction kinetics of As containing Fe-oxides, the sorption of arsenic, the kinetics of siderite precipitation and dissolution, as well as of the dissolution of CaCO3. The arsenic released from the Fe-oxide is preferentially partitioned into the water phase, and partially sorbed, while the released Fe(II) is precipitated as siderite. The reaction network involved in arsenic mobilization was analyzed by 1-D reactive transport modeling. The results reveal complex interactions between the kinetics of organic matter degradation and the kinetics and thermodynamic energy released by Fe-oxide reduction. The energy released by Fe-oxide reduction is strongly pH dependent and both methanogenesis and carbonate precipitation and dissolution have important influences on the pH. Overall it is the rate of organic carbon degradation that determines the total electron flow. However, the kinetics of Fe-oxide reduction determines the distribution of this flow of electrons between methanogenesis, which is by far the main pathway, and Fe-oxide reduction. Modeling the groundwater arsenic content over a 6000 year period in a 20 m thick aquifer shows an increase in As during the first 1200 years where it reaches a maximum of about 600 μg/L. During this initial period the release of arsenic from Fe-oxides actually decreases but the adsorption of arsenic onto the sediment delays the build-up in the groundwater arsenic concentration. After 1200 years the groundwater arsenic content slowly decreases controlled both by desorption and continued further, but diminishing, release from Fe-oxide being reduced. After 6000 years the arsenic content has decreased to 33 μg/L. The modeling enables a quantitative description of how the aquifer properties, the reactivity of organic carbon and Fe-oxides, the number of sorption sites and the buffering mechanisms change over a 6000 year period and how the combined effect of these interacting processes controls the groundwater arsenic content.