Arsenic is a common trace element in groundwater and its fate and transport are controlled by combination of (i) natural processes, including redox conditions, salinity and pH, (ii) sedimentary and geochemical environment, and (iii) anthropogenic influences such as groundwater extraction, managed aquifer recharge (MAR), Aquifer Thermal Energy Storage (ATES), and pollution. We investigated the relative influence of these processes by presenting 10 cases from The Netherlands. Our review showed that the primary controlling factor for arsenic mobility in natural coastal dune systems is the redox state of groundwater, with concentrations between 2 and 10 μg/L. Strongly reduced greensands (containing glauconite and, more importantly, associated minerals) exhibited elevated As concentrations, with concentrations up to 40 μg/L. Groundwater systems modified by MAR or those that are influenced by nitrate pollution (NP) showed elevated As concentrations (20–110 μg/L), as a result of either pyrite oxidation (MAR, NP) or reductive dissolution of iron(hydr)oxides (MAR). Increasing temperature at ATES systems may cause mobilization of As at temperatures beyond 25 °C. The highest As concentrations were observed at sites where muddy sediments were recently deposited in surface water bodies (200–820 μg/L), for example in dammed Rhine River tributaries and sand pit lakes south of the city of Amsterdam. The reduction of arsenate to arsenite and competitive desorption during intrusion of polluted water also form important As mobilizing processes. The data for the Netherlands show that high CH₄ and NH₄ concentrations may form a risk indicator of elevated As levels in some fresh groundwater systems.

Well clogging was studied at an aquifer storage transfer and recovery (ASTR) site used to secure freshwater supply for a flower bulb farm. Tile drainage water (TDW) was collected from a 10-ha parcel, stored in a sandy brackish coastal aquifer via well injection in wet periods, and reused during dry periods. This ASTR application has been susceptible to clogging, as the TDW composition largely exceeded most clogging mitigation guidelines. TDW pretreatment by sand filtration did not cause substantial clogging at a smaller ASR site (2 ha) at the same farm. In the current (10 ha) system, sand filtration was substituted by 40-μm disc filters to lower costs (by 10,000–30,000 Euro) and reduce space (by 50–100 m²). This measure treated TDW insufficiently and injection wells rapidly clogged. Chemical, biological, and physical clogging occurred, as observed from elemental, organic carbon, 16S rRNA, and grain-size distribution analyses of the clogging material. Physical clogging by particles was the main cause, based on the strong relation between injected turbidity load and normalized well injectivity. Periodical backflushing of injection wells improved operation, although the disc filters clogged when the turbidity increased (up to 165 NTU) during a severe rainfall event (44 mm in 3 days). Automated periodical backflushing, together with regulating the maximum turbidity (<20 NTU) of the TDW, protected ASTR operation, but reduced the injected TDW volume by ~20–25%. The studied clogging-prevention measures collectively are only viable as an alternative for sand filtration when the injected volume remains sufficient to secure the farmer’s needs for irrigation.

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.

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.

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. K_oc 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.

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.

Arsenic (As) is a highly toxic element which naturally occurs in drinking water. In spite of substantial evidence on the association between many illnesses and chronic consumption of As, there is still a considerable uncertainty about the health risks due to low As concentrations in drinking water. In the Netherlands, drinking water companies aim to supply water with As concentration of <1 μg/L – a water quality goal which is tenfold more stringent than the current WHO guideline. This paper provides (i) an account on the assessed lung cancer risk for the Dutch population due to pertinent low-level As in drinking water and cost-comparison between health care provision and As removal from water, (ii) an overview of As occurrence and mobility in drinking water sources and water treatment systems in the Netherlands and (iii) insights into As removal methods that have been employed or under investigation to achieve As reduction to <1 µg/L at Dutch water treatment plants. Lowering of the average As concentration to <1μg/L in the Netherlands is shown to result in an annual benefit of 7.2–14 M€. This study has a global significance for setting drinking water As limits and provision of safe drinking water.

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 < 1 kWh/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 ~ 1600 mg/L) in the Damour coastal aquifer in Lebanon. The concept is expected to produce ca. 1000 m³/d of freshwater from this well by pumping 250 m³/d of fresh groundwater from the top well screen and 800 m³/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 4 years 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.

Managed Aquifer Recharge (MAR) is a promising method of increasing water availability in water stressed areas by subsurface infiltration and storage, to overcome periods of drought, and to stabilize or even reverse salinization of coastal aquifers. Moreover, MAR could be a key technique in making alternative water resources available, such as reuse of communal effluents for agriculture, industry and even indirect potable reuse. As exemplified by the papers in this Special Issue, consideration of water quality plays a major role in developing the full potential for MAR application, ranging from the improvement of water quality to operational issues (e.g., well clogging) or sustainability concerns (e.g., infiltration of treated waste water). With the application of MAR expanding into a wider range of conditions, from deserts to urban and coastal areas, and purposes, from large scale strategic storage of desalinated water and the reuse of waste water, the importance of these considerations are on the rise. Addressing these appropriately will contribute to a greater understanding, operational reliability and acceptance of MAR applications, and lead to a range of engineered MAR systems that help increase their effectiveness to help secure the availability of water at the desired quality for the future.

To be able to overcome water shortages, Abu Dhabi Emirate started an Aquifer Storage and Recovery (ASR) project with desalinated seawater (DSW) as source water near Liwa. It is the largest DSW-ASR project in the world (stored volume ~10 Mm³/year), and should recover potable water for direct use. DSW is infiltrated into a desert dune sand aquifer using "sand-covered gravel-bed" recharge basins. In this study, we evaluate the hydrogeological and hydrogeochemical stratification of the (sub)oxic target aquifer, and water quality changes of DSW during trial infiltration runs. We predict water quality changes of DSW after 824 d of infiltration, during 90 d of intensive recovery (67% recovered) without storage (scenario A), as well as after 10 years of storage (scenario B, with significant bubble drift). Monitoring of preceding trials revealed a lack of redox reactions; little carbonate dissolution and Ca/Na exchange; much SiO₂ dissolution; a strong mobilization of natural AsO₄ ^3-, B, Ba, F, CrO₄ ^2-, Mo, Sr and V from the (sub)oxic aquifer; and immobilization of PO₄, Al, Cu, Fe and Ni from DSW. The Easy-Leacher model was applied in forward and reverse mode including lateral bubble drift, to predict water quality of the recovered water. We show that hydrogeochemical modeling of a complex ASR-system can be relatively easy and straightforward, if aquifer reactivity is low and redox reactions can be ignored. The pilot observations and modeling results demonstrate that in scenario A recovered water quality still complies with Abu Dhabi's drinking water standards (even up to 85% recovery). For scenario B, however, the recovery efficiency declines to 60% after which various drinking water standards are exceeded, especially the one for chromium.

This study demonstrates groundwater quality differences between a limestone and a dolomitic limestone, (sub)oxic coastal aquifer in the Eastern Mediterranean (Lebanon), with and without ongoing moderate salinization since the last decades. For this purpose, 8 major and 50 trace elements (TEs) were analyzed in 80 water and 65 rock samples, and interpreted with a quad-fold approach utilizing: (1) nonparametric statistical tests, (2) concentration deviations from ideal conservative freshwater–seawater mixing lines, (3) a new parameter called Mixing Enrichment Factor to assess the mobility of chemical constituents under salinizing conditions, and (4) 1-D dual porosity flow path modeling with PHREEQC. Dissolution/precipitation of Ca_xMg_ySr_zCO₃ and cation exchange were the main disclosed hydrogeochemical processes besides minor signs of organic matter oxidation. In the dolomitic limestone aquifer, less carbonate dissolved as compared to the limestone aquifer, partly because of lower pCO₂ in addition to seawater inflow triggering Mg-calcite precipitation by cation exchange. Saltwater intrusion led to mobilization of As, Ba, Cu, Ni, Rb, Sr and U in both aquifers, sometimes likely by cation exchange (e.g. Ba and Sr). Some of these TEs (notably Cu and Ni) recorded higher concentrations in the dolomitic limestone regardless of salinization. Other elements like Al, Be, Ce, Cr, Nb, Pb, V, Y and Zr revealed no or a low mobilization tendency. The concentration of all TEs in groundwater remained below drinking water limits notwithstanding moderate salinization. This classifies carbonate rocks as a weak geogenic source of TEs, whereas encroaching seawater appears to be a more important source.

Observations are reported on (i) groundwater recharge rates under various types of vegetation as measured with megalysimeters in the dunes, (ii) freshwater lenses along the Dutch North Sea coast in the early 1900s, and (iii) rainwater lenses that develop on top of laterally migrating, artificially recharged riverwater. Subsequently analytical methods are presented to estimate annual natural groundwater recharge as function of rainfall and vegetation, and to calculate the size, shape and transition zone of freshwater lenses on saline groundwater and rainwater lenses on infiltrated riverwater. An empirical correction factor, based on the hydraulic resistance of an aquitard within the freshwater lens, is proposed to account for the frequently observed reduction of the Ghyben-Herzberg ratio of 40. This factor raises the groundwater table, reduces the depth of the fresh/salt interface and increases the lens formation time. The suite of methods offers a tool box for knowledge based water management of dune systems, by rapidly predicting: (i) more or less autonomous changes due to sealevel rise, climate change and vegetation development; and (ii) the potential (side) effects of interventions. Knowing what happened or will happen to the fresh water lens or a rainwater lens is important, because changes impact on important natural habitat parameters such as salinity, depth to groundwater table, decalcification rate (and thus on pH, Ca/Al, PO₄, NH₄) and nutrient availability, and on drinking water supply. The analytical models are applied to predict effects of sealevel rise, coastal progradation, vegetation changes, and increased temperature of coastal air and river water to be infiltrated.

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.

The use of multiple partially penetrating wells (MPPW) during aquifer storage and recovery (ASR) in brackish aquifers can significantly improve the recovery efficiency (RE) of unmixed injected water. The water quality changes by reactive transport processes in a field MPPW-ASR system and their impact on RE were analyzed. The oxic freshwater injected in the deepest of four wells was continuously enriched with sodium (Na⁺) and other dominant cations from the brackish groundwater due to cation exchange by repeating cycles of 'freshening'. During recovery periods, the breakthrough of Na⁺ was retarded in the deeper and central parts of the aquifer by 'salinization'. Cation exchange can therefore either increase or decrease the RE of MPPW-ASR compared to the RE based on conservative Cl^-, depending on the maximum limits set for Na⁺, the aquifer's cation exchange capacity, and the native groundwater and injected water composition. Dissolution of Fe and Mn-containing carbonates was stimulated by acidifying oxidation reactions, involving adsorbed Fe²⁺ and Mn²⁺ and pyrite in the pyrite-rich deeper aquifer sections. Fe²⁺ and Mn²⁺ remained mobile in anoxic water upon approaching the recovery proximal zone, where Fe²⁺ precipitated via MnO₂ reduction, resulting in a dominating Mn²⁺ contamination. Recovery of Mn²⁺ and Fe²⁺ was counteracted by frequent injections of oxygen-rich water via the recovering well to form Fe and Mn-precipitates and increase sorption. The MPPW-ASR strategy exposes a much larger part of the injected water to the deeper geochemical units first, which may therefore control the mobilization of undesired elements during MPPW-ASR, rather than the average geochemical composition of the target aquifer.