Degradation of seven pesticides and two metabolites before and during aquifer storage transfer and recovery operation.

Degradation of 7 common pesticides (bentazon, boscalid, chloridazon, fluopyram, flutolanil, imidacloprid, and methoxyfenozide) and 2 metabolites of chloridazon (desphenyl-chloridazon, and methyl-desphenyl-chloridazon) was studied in an anoxic and brackish sandy aquifer before and during Aquifer Storage Transfer and Recovery (ASTR) operation. Fresh tile drainage water was injected and stored for later re-use as irrigation water. We hypothesized that electron acceptors (O2, NO3), dissolved organic carbon (∼24.7 mg/L), nutrients (NO3: ∼14.1 mg/L, NH4: ∼0.13 mg/L, PO4: ∼5.2 mg/L), and biodegrading bacteria in tile drainage water could stimulate degradation of the pesticides and metabolites (ranging between 0.013 and 10.8 µg/L) introduced in the aquifer. Pesticide degradation was studied at 6 depths in the aquifer using push-pull tests lasting ±18 days before the onset of ASTR operation. Degradation was too limited to quantify and/or could not be assessed because of the potential occurrence of pesticide retardation. Utilizing push-pull tests to obtain degradation constants should only be considered in future studies for non-retarding pesticides with relative low half-lives (here <20 days). During ASTR operation, pesticide degradation was studied at the same depths during 3 storage periods equally spread over 1.5 years of ASTR operation. Overall, trends of degradation were observed, although with relatively high half-lives of at least 53 days. Microbial adaptation of the aquifer and/or bioaugmentation by the injected biodegrading bacteria did not result in enhanced degradation during consecutive storage periods. Operational monitoring data over longer periods and distances yielded half-lives of at least 141 days. The slow degradation mostly agrees with previous studies. The injected tile drainage water composition did therefore not notably stimulate pesticide degradation. The relatively persistent behavior of the studied pesticides/metabolites implies that ASTR abstracted water will have generally high pesticide concentrations, and non-abstracted water may form a contamination risk for the surrounding native brackish groundwater.

Denitrification kinetics during aquifer storage and recovery of drainage water from agricultural land.

An aquifer storage transfer and recovery (ASTR) system was studied in which tile drainage water (TDW) was injected with relatively high NO3 (about 14 mg/L) concentrations originating from fertilizers. Here we present the evolution of denitrification kinetics at 6 different depths in the aquifer before, and during ASTR operation. First-order denitrification rate constants increased over time before and during the first days of ASTR operation, likely due to microbial adaptation of the native bacterial community and/or bioaugmentation of the aquifer by denitrifying bacteria present in injected TDW. Push-pull tests were performed in the native aquifer before ASTR operation. Obtained first-order denitrification rate constants were negligible (0.00-0.03 d-1) at the start, but increased to 0.17-0.83 d-1 after a lag-phase of about 6 days. During the first days of ASTR operation in autumn 2019, the arrival of injected TDW was studied at 2.5 m distance from the injection well. First-order denitrification rate constants increased again over time (maximum >1 d-1). Three storage periods without injection were monitored in winter 2019, fall 2020, and spring 2021 during ASTR operation. First-order rate constants ranged between 0.12 and 0.61 d-1. Denitrification coupled to pyrite oxidation occurred at all depths, but other oxidation processes were indicated as well. NO3 concentration trends resembled Monod kinetics but were fitted also to a first-order decay rate model to facilitate comparison. Rate constants during the storage periods were substantially lower than during injection, probably due to a reduction in the exchange rate between aquifer solid phases and injected water during the stagnant conditions. Denitrification rate constants deviated maximally a factor 5 over time and depth for all in-situ measurement approaches after the lag-phase. The combination of these in-situ approaches enabled to obtain more detailed insights in the evolution of denitrification kinetics during AS(T)R.

Field Testing of a Novel Drilling Technique to Expand Well Diameters at Depth in Unconsolidated Formations.

Larger well diameters allow higher groundwater abstraction rates. But particularly for the construction of wells at greater depth, it may be more cost-efficient to only expand the borehole in the target aquifer. However, current drilling techniques for unconsolidated formations are limited by their expansion factors (<2) and diameters (<1000 mm). Therefore, we developed a new technique aiming to expand borehole diameters at depth in a controlled manner using a low-pressure water jet perpendicular to the drilling direction and extendable by means of a pivoting arm. During a first field test, the borehole diameter was expanded 2.6-fold from 600 to 1570 mm at a depth of 53.5 to 68 m and equipped with a well screen to create an expanded diameter gravel well (EDGW). In keeping with the larger diameter, the volume flux per m screen length was two times higher than conventional 860 mm diameter wells at the site in the subsequent 3 year production period. Although borehole clogging was slower on a volumetric basis and similar when normalized to borehole wall area, rehabilitation of particle clogging at the borehole wall was more challenging due to the thickness of the gravel pack. While jetting the entire borehole wall before backfilling holds promise to remove filter cake and thus limit particle clogging, we found that a second borehole (expanded 4.1-fold to 2460 mm) collapsed during jetting. Overall, the EDGW technique has potential to make the use of deeper unconsolidated aquifers economically (more) feasible, although further understanding of the borehole stability and rehabilitation is required to assess its wider applicability.

Intra aquifer variations in pesticide sorption during a field injection experiment.

A field injection experiment was performed in an anoxic sandy aquifer over 6 days to assess sorption characteristics of 7 commonly applied pesticides in agriculture and 2 frequently detected metabolites. Pesticide use changed considerably in the last decades, and there is insufficient knowledge of the fate of currently used pesticides in aquifers. Injected water arrival was monitored at 6 depth intervals of 1 m ranging from 11.4 to 32.2 m-below surface level with varying organic carbon contents (0.057-0.91%d.w.) to examine intra-aquifer variations in sorption. Observed pesticide concentrations were fit using a non-linear least squares routine to an advection-dispersion equation, from which retardation factors (R) were obtained. Pesticide degradation did not significantly influence the simulated R during the experiment. We observed that bentazon and cycloxydim were most mobile with R < 1.1 at all depths. Desphenyl chloridazon, methyl desphenyl chloridazon, and imidacloprid were, on average, less mobile, with maximum R of 1.5. Boscalid, chloridazon, fluopyram, and flutolanil showed a larger range of R, and R > 2.0 were observed in the shallowest part of the aquifer. Largest R were observed at the top of the aquifer and decreased with depth. Koc values varied similarly, which indicates that sorption is not only influenced by sedimentary organic matter (SOM) content but also by its sorption reactivity. Obtained sorption parameters were substantially lower than reported in a widely used pesticide sorption database, which suggests that sorption parameters are influenced by methodological differences and variations in the sorption reactivity of SOM. The large intra-aquifer variations in pesticide sorption highlights that aquifer heterogeneity should be considered in groundwater risk assessments.

Identification of iron and sulfate release processes during riverbank filtration using chemical mass balance modeling.

Various hydrogeochemical processes can modify the quality of river water during riverbank filtration (RBF). Identifying the subsurface processes responsible for the bank-filtered water quality is challenging, but essential for predicting water quality changes and determining the necessity of post-treatment. However, no systematic approach for this has been proposed yet. In this study, the subsurface hydrogeochemical processes that caused the high concentrations of total iron (Fe) and sulfate (SO42-) in the bank-filtered water were investigated at a pilot-scale RBF site in South Korea. For this purpose, water quality variations were monitored in both the extraction well and the adjacent river over five months. The volumetric mixing ratio between the river water and the native groundwater in the RBF well was calculated to understand the effect of mixing on the quality of water from the well and to assess the potential contribution of subsurface reactions to water quality changes. To identify the subsurface processes responsible for the evolution of Fe and SO42- during RBF, an inverse modeling based on the chemical mass balance was conducted using the water quality data and the calculated volumetric mixing ratio. The modeling results suggest that pyrite oxidation by abundant O2 present in an unsaturated zone could be a primary process explaining the evolution of total Fe and SO42- during RBF at the study site. The presence of pyrite in the aquifer was indirectly supported by iron sulfate hydroxide (Fe(SO4)(OH)) detected in oxidized aquifer sediments.

Transport of bacteriophage MS2 and PRD1 in saturated dune sand under suboxic conditions.

Soil passage of (pretreated) surface water to remove pathogenic microorganisms is a highly efficient process under oxic conditions, reducing microorganism concentrations about 8 log10 within tens of meters. However, under anoxic conditions, it has been shown that removal of microorganisms can be limited very much. Setback distances for adequate protection of natural groundwater may, therefore, be too short if anoxic conditions apply. Because removal of microorganisms under suboxic conditions is unknown, this research investigated removal of bacteriophage MS2 and PRD1 by soil passage under suboxic conditions at field scale. At the field location (dune area), one injection well and six monitoring wells were installed at different depths along three suboxic flow lines, where oxygen concentrations ranged from 0.4 to 1.7 mg/l and nitrate concentrations ranged from 13 to 16 mg/L. PRD1 and MS2 were injected directly at the corresponding depths and their removal in each flow line was determined. The highest bacteriophage removal was observed in the top layer, with about 9 log removal of MS2, and 7 log removal of PRD1 after 16 meters of aquifer transport. Less removal was observed at 12 m below surface, probably due to a higher groundwater velocity in this coarser grained layer. MS2 was removed more effectively than PRD1 under all conditions. Due to short travel times, inactivation of the phages was limited and the reported log removal was mainly associated with attachment of phages to the aquifer matrix. This study shows that attachment of MS2 and PRD1 is similar for oxic and suboxic sandy aquifers, and, therefore, setback distances used for sandy aquifers under oxic and suboxic conditions provide a similar level of safety. Sticking efficiency and the attachment rate coefficient, as measures for virus attachment, were evaluated as a function of the physico-chemical conditions.

Effects of intake interruptions on dune infiltration systems in the Netherlands, their quantification and mitigation.

In the coastal dunes of the Western Netherlands, managed aquifer recharge (MAR) is applied for drinking water supply since 1957. The MAR systems belong to the Aquifer Transfer Recovery (ATR) type, because recharge and recovery are operated without interruption. This makes these systems very vulnerable to intake interruptions, which are expected to increase in frequency and duration due to climate change. Such interruptions are problematic, because: (i) groundwater recovery from dunes needs to continue to supply fresh drinking water to the Western Netherlands; (ii) risks of salt water intrusion are high, and (iii) MAR bordering wet dune slacks with an EU Natura 2000 status cannot survive for long without MAR. In this paper, effects of intake stops are discussed and quantified. The hydrological effects consist of the decline of water tables, disappearance of flow-through dune lakes, reservoir depletion, salt water intrusion, disruption of rainwater lenses, and entrapped air hampering a rapid refill of the groundwater reservoir. Water quality effects include changes in (i) redox environment of the flushed aquifer, impacting the behavior of nutrients, calcium, sulfate and organic micro-pollutants, and (ii) the mixing ratio of water types. The main ecological impacts comprise the dying of organisms in recharge ponds and dune lakes, and a decline of biodiversity. Effects of very long intake interruptions (years) are predicted via historical observations during the long overexploitation period (1900-1957) prior to MAR. A closed form analytical solution for safe yield of a semiconfined aquifer is proposed, together with a related upconing risk index. Both also apply to the pumping from any fresh water lens without MAR. Some mitigation strategies are discussed, such as a dual intake, raising the storage capacity, earlier mud removal, and accelerated refilling of the reservoir. A magnitude scale for intake stops (MIS) is proposed.

Mitigation of saltwater intrusion by 'integrated fresh-keeper' wells combined with high recovery reverse osmosis.

Most countermeasures to mitigate saltwater intrusion in coastal, karstic or fractured aquifers are hindered by anisotropy, high transmissivities and complex dynamics. A coupled strategy is introduced here as a localized remedy to protect shallow freshwater reserves while utilizing the deeper intercepted brackish water. It is a double sourcing application where fresh-keeper wells are installed at the bottom of a deepened borehole of selected salinized wells, and then supported by high recovery RO desalination. The RO design has <1kWh/m3 energy consumption, and up to 96% recovery in addition to low scaling propensity without use of any anti-scalant. A feasibility study is presented as an example for a salinizing, brackish well (TDS ~1600mg/L) in the Damour coastal aquifer in Lebanon. The concept is expected to produce ca. 1000m3/d of freshwater from this well by pumping 250m3/d of fresh groundwater from the top well screen and 800m3/d of brackish groundwater (to be later desalinized) from the fresh-keeper well screen below. Cost analysis shows that the capital cost could be returned back in 1 to 4years depending on the choice of produced water (bottled or tap) and available market. As an alternative, water from the RO plant could be blended with lower quality water, for instance untreated brackish groundwater (if unpolluted), to supply 3 more volumes for domestic use. The usage of brackish groundwater from integrated fresh-keeper wells thus serves 3 purposes: production of high quality drinking water, financial gain and mitigation of water stress by overpumping.

The fate of organic micropollutants during long-term/long-distance river bank filtration.

The fate of organic micropollutants during long-term/long-distance river bank filtration (RBF) at a temporal scale of several years was investigated along a row of monitoring wells perpendicular to the Lek River (the Netherlands). Out of 247 compounds, which were irregularly analyzed in the period 1999-2013, only 15 were detected in both the river and river bank observation wells. Out of these, 10 compounds (1,4-dioxan, 1,5-naphthalene disulfonate (1,5-NDS), 2-amino-1,5-NDS, 3-amino-1,5-NDS, AOX, carbamazepine, EDTA, MTBE, toluene and triphenylphosphine oxide) showed fully persistent behavior (showing no concentration decrease at all), even after 3.6 years transit time. The remaining 5 compounds (1,3,5-naphthalene trisulfonate (1,3,5-NTS), 1,3,6-NTS, diglyme, iopamidol, triglyme) were partially removed. Their reactive transport parameters (removal rate constants/half-lives, retardation coefficients) were inferred from numerical modeling. In addition, maximum half-lives for 14 of the fully removed compounds, for which the data availability was sufficient to deduce 100% removal during sub-surface passage, were approximated based on travel times to the nearest well. The study is one of very few reporting on the long-term field-scale behavior of organic micropollutants. It highlights the efficiency of RBF for water quality improvement as a pre-treatment step for drinking water production. However, it also shows the very persistent behavior of various compounds in groundwater.

Reactive transport modeling of thermal column experiments to investigate the impacts of aquifer thermal energy storage on groundwater quality.

Aquifer thermal energy storage (ATES) systems are increasingly being used to acclimatize buildings and are often constructed in aquifers used for drinking water supply. This raises the question of potential groundwater quality impact. Here, we use laboratory column experiments to develop and calibrate a reactive transport model (PHREEQC) simulating the thermally induced (5-60 °C) water quality changes in anoxic sandy sediments. Temperature-dependent surface complexation, cation-exchange, and kinetic dissolution of K-feldspar were included in the model. Optimization results combined with an extensive literature survey showed surface complexation of (oxy)anions (As, B, and PO4) is consistently exothermic, whereas surface complexation of cations (Ca and Mg) and cationic heavy metals (Cd, Pb, and Zn) is endothermic. The calibrated model was applied to simulate arsenic mobility in an ATES system using a simple yet powerful mirrored axi-symmetrical grid. Results showed that ATES mobilizes arsenic toward the fringe of the warm water bubble and the center of the cold water bubble. This transient redistribution of arsenic causes its aqueous concentrations in the cold and warm groundwater bubbles to become similar through multiple heating cycles, with a final concentration depending on the average injection temperature of the warm and cold ATES wells.

Impacts of shallow geothermal energy production on redox processes and microbial communities.

Shallow geothermal systems are increasingly being used to store or harvest thermal energy for heating or cooling purposes. This technology causes temperature perturbations exceeding the natural variations in aquifers, which may impact groundwater quality. Here, we report the results of laboratory experiments on the effect of temperature variations (5-80 °C) on redox processes and associated microbial communities in anoxic unconsolidated subsurface sediments. Both hydrochemical and microbiological data showed that a temperature increase from 11 °C (in situ) to 25 °C caused a shift from iron-reducing to sulfate-reducing and methanogenic conditions. Bioenergetic calculations could explain this shift. A further temperature increase (>45 °C) resulted in the emergence of a thermophilic microbial community specialized in fermentation and sulfate reduction. Two distinct maxima in sulfate reduction rates, of similar orders of magnitude (5 × 10(-10) M s(-1)), were observed at 40 and 70 °C. Thermophilic sulfate reduction, however, had a higher activation energy (100-160 kJ mol(-1)) than mesophilic sulfate reduction (30-60 kJ mol(-1)), which might be due to a trade-off between enzyme stability and activity with thermostable enzymes being less efficient catalysts that require higher activation energies. These results reveal that while sulfate-reducing functionality can withstand a substantial temperature rise, other key biochemical processes appear more temperature sensitive.

Temperature-induced impacts on groundwater quality and arsenic mobility in anoxic aquifer sediments used for both drinking water and shallow geothermal energy production.

Aquifers used for the production of drinking water are increasingly being used for the generation of shallow geothermal energy. This causes temperature perturbations far beyond the natural variations in aquifers and the effects of these temperature variations on groundwater quality, in particular trace elements, have not been investigated. Here, we report the results of column experiments to assess the impacts of temperature variations (5°C, 11°C, 25°C and 60°C) on groundwater quality in anoxic reactive unconsolidated sandy sediments derived from an aquifer system widely used for drinking water production in the Netherlands. Our results showed that at 5 °C no effects on water quality were observed compared to the reference of 11°C (in situ temperature). At 25°C, As concentrations were significantly increased and at 60 °C, significant increases were observed pH and DOC, P, K, Si, As, Mo, V, B, and F concentrations. These elements should therefore be considered for water quality monitoring programs of shallow geothermal energy projects. No consistent temperature effects were observed on Na, Ca, Mg, Sr, Fe, Mn, Al, Ba, Co, Cu, Ni, Pb, Zn, Eu, Ho, Sb, Sc, Yb, Ga, La, and Th concentrations, all of which were present in the sediment. The temperature-induced chemical effects were probably caused by (incongruent) dissolution of silicate minerals (K and Si), desorption from, and potentially reductive dissolution of, iron oxides (As, B, Mo, V, and possibly P and DOC), and mineralisation of sedimentary organic matter (DOC and P).

Perfluorinated alkylated acids in groundwater and drinking water: identification, origin and mobility.

Human exposure to perfluorinated alkylated acids (PFAA) occurs primarily via the dietary intake and drinking water can contribute significantly to the overall PFAA intake. Drinking water is produced from surface water and groundwater. Waste water treatment plants have been identified as the main source for PFAA in surface waters and corresponding drinking water. However, even though groundwater is an important source for drinking water production, PFAA sources remain largely uncertain. In this paper, we identified different direct and indirect sources of PFAA to groundwater within the catchment area of a public supply well field (PSWF) in The Netherlands. Direct sources were landfill leachate and water draining from a nearby military base/urban area. Indirect sources were infiltrated rainwater. Maximum concentrations encountered in groundwater within the landfill leachate plume were 1.8 µg/L of non branched perfluorooctanoic acid (L-PFOA) and 1.2 µg/L of perfluorobutanoic acid (PFBA). Sum concentrations amounted to 4.4 µg/L total PFAA. The maximum concentration of ΣPFAA in the groundwater originating from the military camp was around 17 ng/L. Maximum concentrations measured in the groundwater halfway the landfill and the PWSF (15 years travel distance) were 29 and 160 ng/L for L-PFOA and PFBA, respectively. Concentrations in the groundwater pumping wells (travel distance >25 years) were much lower: 0.96 and 3.5 ng/L for L-PFOA and PFBA, respectively. The chemical signature of these pumping wells corresponded to the signature encountered in other wells sampled which were fed by water that had not been in contact with potential contaminant sources, suggesting a widespread diffuse contamination from atmospheric deposition.

Perfluorinated compounds in infiltrated river rhine water and infiltrated rainwater in coastal dunes.

Different studies have shown that surface waters contain perfluorinated compounds (PFCs) in the low ng/L range. Surface waters are used to produce drinking water and PFCs have been shown to travel through the purification system and form a potential threat to human health. The specific physicochemical properties of PFCs cause them to be persistent and some of them to be bioaccumulative and toxic in the environment. This study investigates the evolvement of PFC concentrations in Rhine water and rainwater during dune water infiltration processes over a transect in the dune area of the western part of The Netherlands. The difference between infiltrated river water and rainwater in terms of PFC composition was investigated. Furthermore, isomer profiles were investigated. The compound perfluorobutanesulfonate (PFBS) was found at the highest concentrations of all PFCs investigated, up to 37 ng/L in infiltrated river water (71 ± 13% of ΣPFCs). This is in contrast with the predominant occurrence of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) reported in literature. The concentrations of PFBS found in infiltrated river Rhine water were significantly higher than those in infiltrated rainwater. For perfluorohexanesulfonate (PFHxS) the opposite was found: infiltrated rainwater contained more than infiltrated river water. The concentrations of PFOA, perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), PFBS, PFOS, and PFHxS in infiltrated river water showed an increasing trend with decreasing age of the water. The relative contribution of the branched PFOA and PFOS isomers to total concentrations of PFOA and PFOS showed a decreasing trend with decreasing age of the water.

Evaluation of conceptual and numerical models for arsenic mobilization and attenuation during managed aquifer recharge.

Managed Aquifer Recharge (MAR) is promoted as an attractive technique to meet growing water demands. An impediment to MAR applications, where oxygenated water is recharged into anoxic aquifers, is the potential mobilization of trace metals (e.g., arsenic). While conceptual models for arsenic transport under such circumstances exist, they are generally not rigorously evaluated through numerical modeling, especially at field-scale. In this work, geochemical data from an injection experiment in The Netherlands, where the introduction of oxygenated water into an anoxic aquifer mobilized arsenic, was used to develop and evaluate conceptual and numerical models of arsenic release and attenuation under field-scale conditions. Initially, a groundwater flow and nonreactive transport model was developed. Subsequent reactive transport simulations focused on the description of the temporal and spatial evolution of the redox zonation. The calibrated model was then used to study and quantify the transport of arsenic. In the model that best reproduced field observations, the fate of arsenic was simulated by (i) release via codissolution of arsenopyrite, stoichiometrically linked to pyrite oxidation, (ii) kinetically controlled oxidation of dissolved As(III) to As(V), and (iii) As adsorption via surface complexation on neo-precipitated iron oxides.

Identification of temperature-dependent water quality changes during a deep well injection experiment in a pyritic aquifer.

Artificial recharge is a technique used increasingly to supplement drinking water supplies. To assess the potential water quality changes that occur during subsurface passage, a comprehensive deep-well injection experiment was carried out for a recharge scheme, where pretreated, aerobic surface water was injected at 300 m depth into an anaerobic aquifer. Water quality parameters were recorded over the 854-days long injection phase. The evolution of the major ion and redox chemistry was analyzed with a three-dimensional reactive multicomponent transport model. It was found that the oxidation of pyrite was the main driverforwater quality changes and that reaction rates depended significantly on the spatially/temporally varying groundwater temperature. With the temperature-dependency of the oxidation reactions incorporated into the model, the simulations give an accurate picture of the temporal and spatial evolution of the hydrochemical changes that occurred during the experiment. To delineate the influence of physical and chemical processes on local concentration changes the results of the reactive transport model simulations were compared with the corresponding results from nonreactive simulations. The study emphasizes the suitability of mechanistic multicomponent reactive transport modeling as an integrative tool for data analysis when physical transport and chemical processes interact.

Analysis of a deep well recharge experiment by calibrating a reactive transport model with field data.

This paper describes the modeling of the hydrogeochemical effects of deep well recharge of oxic water into an anoxic pyrite-bearing aquifer. Kinetic expressions have been used for mineral dissolution-precipitation rates and organic matter oxidation. Hydrological and chemical parameters of the model were calibrated to field measurements. The results showed that oxidation of pyrite (FeS(2)) and, to a lesser extent, organic matter dominate the changes in quality of the recharged water during its passage through the aquifer. The recharge leads to the consumption of oxygen and nitrate and the formation of sulfate and ferrihydrite. Complexation reactions, cation exchange and precipitation and dissolution of calcite, siderite and rhodochrosite were also identified through the modeling. Despite problems of non-uniqueness of the calibrated parameters, the model was used successfully to depict the geochemical processes occurring in the aquifer. Non-uniqueness can be avoided by constraining the model as much as possible to measurements and/or data from literature, although they cannot be considered always as fixed values and should be considered as stochastic variables instead.