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Geogenic arsenic (As) in groundwater is widespread, affecting drinking water and irrigation supplies globally, with food security and safety concerns on the rise. Here, we present push-pull tests that demonstrate field-scale As immobilization through the injection of small amounts of ferrous iron (Fe) and nitrate, two readily available agricultural fertilizers. Such injections into an aquifer with As-rich (200 ± 52 μg/L) reducing groundwater led to the formation of a regenerable As reactive filter in situ, producing 15 m 3 of groundwater meeting the irrigation water quality standard of 50 μg/L. Concurrently, sediment magnetic properties were markedly enhanced around the well screen, pointing to neo-formed magnetite-like minerals. A reactive transport modeling approach was used to quantitatively evaluate the experimental observations and assess potential strategies for larger-scale implementation. The modeling results demonstrate that As removal was primarily achieved by adsorption onto neo-formed minerals and that an increased adsorption site density coincides with the finer-grained textures of the target aquifer. Up-scaled model simulations with 80-fold more Fe-nitrate reactants suggest that enough As-safe water can be produced to irrigate 1000 m 2 of arid land for one season of water-intense rice cultivation at a low cost without causing undue contamination in surface soils that threatens agricultural sustainability.

Managed aquifer recharge (MAR) is an increasingly used water management technique that enhances water availability while commonly generating water quality benefits. However, MAR activities may also trigger adverse geochemical reactions, especially during the injection of oxidant-enriched waters into reducing aquifers. Where this occurs, the environmental risks and the viability of mitigating them must be well understood. Here, we develop a rigorous approach for assessing and managing the risks from MAR-induced metal mobilization. First, we develop a process-based reactive transport model to identify and quantify the main hydrogeochemical drivers that control the release of metals and their mobility. We then apply a probabilistic framework to interrogate the inherent uncertainty associated with adjustable model parameters and consider this uncertainty (i) in long-term predictions of groundwater quality changes and (ii) in scenarios that investigate the effectiveness of modifications in the water treatment process to mitigate metal release and mobility. The results suggested that Co, Ni, Zn, and Mn were comobilized during pyrite oxidation and that metal mobility was controlled (i) by the sediment pH buffering capacity and (ii) by the sorption capacity of the native aquifer sediments. Both tested mitigation strategies were shown to be effective at reducing the risk of elevated metal concentrations.

The mobility of molybdenum (Mo) in groundwater systems has received little attention, although a high intake of Mo is known to be detrimental to human and animal health. Here, we used a comprehensive hydrochemical data set collected during a multi-cycle aquifer storage and recovery test to study the mechanisms that control the mobility of Mo under spatially and temporally varying hydrochemical conditions. The model-based interpretation of the data indicated that the initial mobilization of Mo occurs as a sequence of reactions, in which (i) the aerobic injectant induces pyrite oxidation, (ii) the released acidity is partially buffered by the dissolution of dolomite that (iii) leads to the release of Mo with highly soluble sulfurized organic matter prevailing between the intercrystalline spaces of the dolomite matrix or incorporated in dolomite crystals. Once released, Mo mobility was primarily controlled by pH-dependent surface complexation reactions to the sediments and, to a lesser extent, the capture by iron sulfides (FeS). In the studied system, Mo mobilization could be effectively mitigated by reducing or eliminating pyrite oxidation, which decreases the likelihood of dolomite dissolution and associated Mo release.

Contamination through per-and poly-fluoroalkyl substances (PFAS) have occurred globally in soil and groundwater systems at military, airport and industrial sites due to the often decades-long periodic application of firefighting foams. At PFAS contaminated sites, the unsaturated soil horizon often serves as a long-term source for sustained PFAS contamination for both groundwater and surface water runoff. An understanding of the processes controlling future mass loading rates to the saturated zone from these source zones is imperative to design efficient remediation measures. In the present study, hydrochemical data from a site where PFAS transport was observed as a result of the decades-long application of AFFF were used to develop and evaluate conceptual and numerical models that determine PFAS mobility across the vadose zone under realistic field-scale conditions. The simulation results demonstrate that the climate-driven physical flow processes within the vadose zone exert a dominating control on the retention of PFAS. Prolonged periods of evapotranspiration exceeding rainfall under the semi-arid conditions trigger periods of upward flux and evapoconcentration, leading to the observed persistence of PFAS compounds in the upper ca. 2 metres of the vadose zone, despite cessation of AFFF application to soils since more than a decade. Physico-chemical retention mechanisms, namely sorption to the air-water interface (AWI) and sediment surfaces, contribute further to PFAS retention. The simulations demonstrate how PFAS downward transport is effectively confined to short periods following discrete rain events when soils display a high degree of saturation. During these periods, AWI sorption is at a minimum. In addition, high PFAS concentrations measured and simulated below the source zone reduce the effect of the AWI further due to a decrease in surface tension associated with elevated PFAS concentrations. Consequently, time-integrated PFAS migration and retardation illuminates that the field-relevant PFAS transport rates are predominantly controlled by the physical flow processes with a lower relative importance of AWI and sediment sorption adding to PFAS retention., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Ltd.)

The injection of oxygenated water into anoxic aquifers during managed aquifer recharge (MAR) can cause the mobilization of metal(loid)s. Here, we study the processes controlling MAR-induced molybdenum (Mo) release in dolomitic aquifers. Sequential chemical extractions and energy dispersive X-ray spectroscopy combined with scanning electron microscopy point to an association of Mo with easily soluble sulfurized organic matter present in intercrystalline spaces of dolomites or directly incorporated within dolomite crystals. The easily soluble character was confirmed by a batch experiment that demonstrated the rapid mobilization of Mo, dissolved organic carbon, and sulfur. The type and time of batch solution contact with the sulfurized organic matter impacted the release of Mo, as demonstrated by a 36% increase in Mo concentrations when shaking was intensified. Based on the experimental results, a conceptual model for the release of Mo was formulated, where (i) the injection of oxygenated water causes the oxidation of pyrite in the aquifer matrix, and (ii) the associated release of protons (H + ) induces the dissolution of dolomite as a buffering reaction, which (iii) enhances the accessibility of the injectant to intercrystalline and incorporated sulfurized organic matter within dolomite, causing the release of Mo.

The occurrence of excessive ammonium in groundwater threatens human and aquatic ecosystem health across many places worldwide. As the fate of ammonium in groundwater systems is often affected by a complex mixture of transport and biogeochemical transformation processes, identifying the sources of groundwater ammonium is an important prerequisite for planning effective mitigation strategies. Elevated ammonium was found in both a shallow and an underlying deep groundwater system in an alluvial aquifer system beneath an agricultural area in the central Yangtze River Basin, China. In this study we develop and apply a novel, indirect approach, which couples the random forest classification (RFC) of machine learning method and fluorescence excitation-emission matrices with parallel factor analysis (EEM-PARAFAC), to distinguish multiple sources of ammonium in a multi-layer aquifer. EEM-PARAFAC was applied to provide insights into potential ammonium sources as well as the carbon and nitrogen cycling processes affecting ammonium fate. Specifically, RFC was used to unravel the different key factors controlling the high levels of ammonium prevailing in the shallow and deep aquifer sections, respectively. Our results reveal that high concentrations of ammonium in the shallow groundwater system primarily originate from anthropogenic sources, before being modulated by intensive microbially mediated nitrogen transformation processes such as nitrification, denitrification and dissimilatory nitrate reduction to ammonium (DNRA). By contrast, the linkage between high concentrations of ammonium and decomposition of soil organic matter, which ubiquitously contained nitrogen, suggested that mineralization of soil organic nitrogen compounds is the primary mechanism for the enrichment of ammonium in deeper groundwaters., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Iodine is an essential micronutrient in the human diet and an appropriate human iodine intake level is important for population health. Excessive iodine intake is often associated with high iodine groundwater which serves as an important drinking water source in many regions. This study aims to identify the source and key hydrogeochemical processes for iodine accumulation and mobility in the groundwaters of the Northern Jiangsu Yishusi Plain. Combined hydrogeochemical and statistical analyses, specifically random forest modeling and factor analysis, were used to explore the mechanisms affecting the spatial distribution of iodine. The concentration of iodine in the investigated groundwaters was found to vary widely and to range between 4.8 and 4750 μg/L, with 48.9% of the total samples (674) exceeding the threshold value of 100 μg/L for toxic exposure, as defined by the Chinese high‑iodine standard guideline. High iodine concentrations are shown to mainly occur in the marine plain and the shallow aquifer associated with the floodplains of the Old Yellow River. The marine or lagoons-facies sediments were identified as the most plausible iodine source. In addition, mixing of groundwater with paleo-seawater might also have played a role in the coastal area. In contrast, the flood sediments of the Old Yellow River are shown to be an unlikely source. However, they serve as a cover layer that favored the development of reducing hydrogeochemical conditions that can trigger iodine mobilization via the reductive dissolution of iron oxides and the degradation of organic matter. Slow groundwater flow rates also appear to favor iodine release from sediments., (Copyright © 2021 Elsevier B.V. All rights reserved.)

High arsenic (As) concentrations in groundwater are a worldwide problem threatening the health of millions of people. Microbial processes are central in the (trans)formation of the As-bearing ferric and ferrous minerals, and thus regulate dissolved As levels in many aquifers. Mineralogy, microbiology and dissolved As levels can vary sharply within aquifers, making high-resolution measurements particularly valuable in understanding the linkages between them. We conducted a high spatial resolution geomicrobiological study in combination with analysis of sediment chemistry and mineralogy in an alluvial aquifer system affected by geogenic As in the Red River delta in Vietnam. Microbial community analysis revealed a dominance of fermenters, methanogens and methanotrophs whereas sediment mineralogy along a 46 m deep core showed a diversity of Fe minerals including poorly crystalline Fe (II/III) and Fe(III) (oxyhydr)oxides such as goethite, hematite, and magnetite, but also the presence of Fe(II)-bearing carbonates and sulfides which likely formed as a result of microbially driven organic carbon (OC) degradation. A potential important role of methane (CH 4 ) as electron donor for reductive Fe mineral (trans)formation was supported by the high abundance of Candidatus Methanoperedens, a known Fe(III)-reducing methanotroph. Overall, these results imply that OC turnover including fermentation, methanogenesis and CH 4 oxidation are important mechanisms leading to Fe mineral (trans)formation, dissolution and precipitation, and thus indirectly affecting As mobility by changing the Fe-mineral inventory., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Geogenic arsenic (As) contamination of groundwater is a health threat to millions of people worldwide, particularly in alluvial regions of South and Southeast Asia. Mitigation measures are often hindered by high heterogeneities in As concentrations, the cause(s) of which are elusive. Here we used a comprehensive suite of stable isotope analyses and hydrogeochemical parameters to shed light on the mechanisms in a typical high-As Holocene aquifer near Hanoi where groundwater is advected to a low-As Pleistocene aquifer. Carbon isotope signatures (δ 13 C-CH 4 , δ 13 C-DOC, δ 13 C-DIC) provided evidence that fermentation, methanogenesis and methanotrophy are actively contributing to the As heterogeneity. Methanogenesis occurred concurrently where As levels are high (>200 µg/L) and DOC-enriched aquitard pore water infiltrates into the aquifer. Along the flowpath to the Holocene/Pleistocene aquifer transition, methane oxidation causes a strong shift in δ 13 C-CH 4 from -87‰ to +47‰, indicating high reactivity. These findings demonstrate a previously overlooked role of methane cycling and DOC infiltration in high-As aquifers., (Copyright © 2021. Published by Elsevier Ltd.)

Fluoride-bearing apatite minerals such as fluorapatite (FAP: Ca 10 (PO 4 ) 6 F 2 ) and related carbonate-rich fluorapatites (CFA: Ca 10 (PO 4 ) 5 (CO 3 ,F)F 2 ), which occur ubiquitously as trace components of rocks and sediments, may act as sources for geogenic groundwater fluoride contamination. CFA dissolution often occurs in conjunction with declining dissolved calcium concentrations. Therefore, managed aquifer recharge (MAR) operations using deionised or low calcium source water are at risk of disturbing the naturally persisting geochemical equilibrium between CFA and the ambient groundwater and induce fluoride mobilisation. In this study, we employ reactive transport modelling to investigate how an engineered manipulation of the MAR source water composition might mitigate such groundwater fluoride contamination. Based on a previously developed and calibrated model for Australia's largest groundwater replenishment operation, we investigate the efficiency of (i) raising aqueous calcium concentration through the addition of CaCl 2 or Ca(OH) 2 amendment, (ii) raising aqueous sodium concentrations through the addition of NaCl or sea salt amendment and (iii) raising the pH. The modelling results illustrate in detail how the geochemical zonation around injection boreholes evolves over time and how this affects fluoride release and attenuation for the different amendment types. Treatments involving the addition of calcium and sodium in the source water are both found to be effective at reducing maximum groundwater fluoride concentrations during MAR, with calcium generally producing the greatest reduction in maximum fluoride concentrations. In contrast, increasing the injectate pH was found to be inefficient in reducing fluoride concentrations significantly due to the strong pH buffering effect of the aquifer sediments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier Ltd.)

Population growth and climate variability highlight the need to enhance freshwater security and diversify water supplies. Subsurface storage of water in depleted aquifers is increasingly used globally to alleviate disparities in water supply and demand often caused by climate extremes including floods and droughts. Managed aquifer recharge (MAR) stores excess water supplies during wet periods via infiltration into shallow underlying aquifers or direct injection into deep aquifers for recovery during dry seasons. Additionally, MAR can be designed to improve recharge water quality, particularly in the case of soil aquifer treatment and riverbank filtration. While there are many potential benefits to MAR, introduction of recharge water can alter the native geochemical and hydrological conditions in the receiving aquifer, potentially mobilizing toxic, naturally occurring (geogenic) contaminants from sediments into groundwater where they pose a much larger threat to human and ecosystem health. On the basis of the present literature, arsenic poses the most widespread challenge at MAR sites due to its ubiquity in subsurface sediments and toxicity at trace concentrations. Other geogenic contaminants of concern include fluoride, molybdenum, manganese, and iron. Water quality degradation threatens the viability of some MAR projects with several sites abandoning operations due to arsenic or other contaminant mobilization. Here, we provide a critical review of studies that have uncovered the geochemical and hydrological mechanisms controlling mobilization of arsenic and other geogenic contaminants at MAR sites worldwide, including both infiltration and injection sites. These mechanisms were evaluated based on site-specific characteristics, including hydrological setting, native aquifer geochemistry, and operational site parameters (e.g., source of recharge water and recharge/recovery cycling). Observed mechanisms of geogenic contaminant mobilization during MAR via injection include shifting redox conditions and, to a lesser extent, pH-promoted desorption, mineral solubility, and competitive ligand exchange. The relative importance of these mechanisms depends on various site-specific, operational parameters, including pretreatment of injection water and duration of injection, storage, and recovery phases. This critical review synthesizes findings across case studies in various geochemical, hydrological, and operational settings to better understand controls on arsenic and other geogenic contaminant mobilization and inform the planning and design of future MAR projects to protect groundwater quality. This critical review concludes with an evaluation of proposed management strategies for geogenic contaminants and identification of knowledge gaps regarding fate and transport of geogenic contaminants during MAR.

Managed aquifer recharge (MAR) enhances freshwater security and augments local groundwater supplies. However, geochemical and hydrological shifts during MAR can release toxic, geogenic contaminants from sediments to groundwater, threatening the viability of MAR as a water management strategy. Using reactive transport modeling coupled with aquifer analyses and measured water chemistry, we investigate the causal mechanisms of arsenic release during MAR via injection in the Orange County Groundwater Basin. Here, injection water is oxygenated, highly purified recycled water produced by advanced water treatment. Injection occurs via a well screened at several depth intervals ranging from 160-365 m, allowing recharge into multiple confined horizons (zones) of the aquifer system. However, these zones are characterized by varying degrees of prior oxidation due to historic, long-term infiltration from the overlying aquifer. The resulting sediment geochemical heterogeneity provides a critical control on the release (or retention) of arsenic. In zones with prior oxidation, As mobilization occurs via arsenate desorption from Fe-(hydr)oxides, primarily associated with shifts in pH; within zones that remain reduced prior to injection, As release is attributed to the oxidative dissolution of As-bearing pyrite. We find that As release can be attributed to various geochemical mechanisms within a single injection well owing to geochemical heterogeneity across the aquifer system.

In water-scarce areas, the reclamation of wastewater through advanced water treatment and subsequent reinjection into depleted aquifers is an increasingly attractive water management option. However, such injection can trigger a range of water-sediment interactions which need to be well understood and quantified to ensure sustainable operations. In this study, reactive transport modeling was used to analyze and quantify the interacting hydrogeochemical processes controlling the mobilization of fluoride and phosphate during injection of highly treated recycled water into a siliciclastic aquifer. The reactive transport model explained the field-observed fluoride and phosphate transport behavior as a result of the incongruent dissolution of carbonate-rich fluorapatite where (i) a rapid proton exchange reaction primarily released fluoride and calcium, and (ii) equilibrium with a mineral-water interface layer of hydrated dibasic calcium phosphate released phosphate. The modeling results illustrated that net exchange of calcium on cation exchange sites in the sediments postbreakthrough of the injectant was responsible for incongruent mineral dissolution and the associated fluoride and phosphate release. Accordingly, amending calcium chloride into the injectant could potentially reduce fluoride and phosphate mobilization at the study site. Insights from this study are broadly applicable to understanding and preventing geogenic fluoride mobilization from fluoride-bearing apatite minerals in many other aquifers worldwide.

During the First Gulf War (1991) a large number of oil wells were destroyed and oil fires subsequently extinguished with seawater. As a result Kuwait's sparse fresh groundwater resources were severely contaminated with crude oil. Since then limited research has focused on the microbial community ecology of the groundwater and their impact on the associated contamination. Here, the microbial community ecology (bacterial, archaeal and eukaryotic) and how it relates to the characteristics of the hydrocarbon contaminants were examined for the first time since the 1991 event. This study was conducted using 15 wells along the main groundwater flow direction and detected several potential hydrocarbon degrading microorganisms such as Hyphomicrobiaceae, Porphyromonadaceae and Eurotiomycetes. The beta diversity of the microbial communities correlated significantly with total petroleum hydrocarbon (TPH) concentrations and salinity. The TPH consisted mainly of polar compounds present as an unresolved complex mixture (UCM) of a highly recalcitrant nature. Based on the proportions of TPH to dissolved organic carbon (DOC), the results indicate that some minor biodegradation has occurred within highly contaminated aquifer zones. However, overall the results from this study suggest that the observed variations in TPH concentrations among the sampled wells are mainly induced by mixing/dilution with pristine groundwater rather than by biodegradation of the contaminants. The findings make an important contribution to better understand the fate of the groundwater pollution in Kuwait, with important implications for the design of future remediation efforts., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Coal seam gas (CSG) extraction generates large volumes of coproduced water. Injection of the excess water into deep aquifers is often the most sustainable management option. However, such injection risks undesired sediment-water interactions that mobilize metal(loid)s in the receiving aquifer. This risk can be mitigated through pretreatment of the injectant. Here, we conducted a sequence of three push-pull tests (PPTs) where the injectant was pretreated using acid amendment and/or deoxygenation to identify the processes controlling the fate of metal(loid)s and to understand the treatment requirements for large-scale CSG water injection. The injection and recovery cycles were closely monitored, followed by analysis of the observations through reactive transport modeling. While arsenic was mobilized in all three PPTs, significantly lower arsenic concentrations were observed in the recovered water when the injectant was deoxygenated, regardless of pH adjustment. The breakthrough of arsenic was commensurate with molybdenum, but distinct from phosphate. This allowed for the observed and modeled arsenic and molybdenum mobilization to be attributed to a stoichiometric codissolution process during pyrite oxidation, whereas phosphate mobility was governed by sorption. Understanding the nature of these hydrochemical processes explained the greater efficiency of pretreatment by deoxygenation on minimizing metal(loid) mobilization compared to the acid amendment.

Over the last few decades, significant progress has been made to characterize the extent, severity, and underlying geochemical processes of groundwater arsenic (As) pollution in S/SE Asia. However, comparably little effort has been made to merge the findings into frameworks that allow for a process-based quantitative analysis of observed As behavior and for predictions of its long-term fate. This study developed field-scale numerical modeling approaches to represent the hydrochemical processes associated with an in situ field injection of reactive organic carbon, including the reductive dissolution and transformation of ferric iron (Fe) oxides and the concomitant release of sorbed As. We employed data from a sucrose injection experiment in the Bengal Delta Plain to guide our model development and to constrain the model parametrization. Our modeling results illustrate that the temporary pH decrease associated with the sucrose transformation and mineralization caused pronounced, temporary shifts in the As partitioning between aqueous and sorbed phases. The results also suggest that while the reductive dissolution of Fe(III) oxides reduced the number of sorption sites, a significant fraction of the released As was rapidly scavenged through coprecipitation with neo-formed magnetite. These secondary reactions can explain the disparity between the observed Fe and As behavior.

The transport and biochemical transformations of the iodinated X-ray contrast medium (ICM) iomeprol were studied at the stream/groundwater interface. During a one-month field experiment piezometric pressure heads, temperatures, and concentrations of redox-sensitive species, iomeprol and 15 of its transformation products (TPs) were collected in stream- and groundwater. The data set was analyzed and transformation processes and rates identified by comparing conservative and reactive transport simulations. ICM and TP transformations were simulated as a cometabolic process during organic carbon degradation. Using iomeprol/TPs ratios as calibration constrain mitigated the uncertainties associated with the high variability of the ICM wastewater discharge into the investigated stream. The study provides evidence that biodegradation of ICM occurs at the field-scale also for predominantly denitrifying conditions. Under these anaerobically dominated field conditions shortest simulated half-life (21 days) was in the same range as previously reported laboratory-determined half-lives for aerobic conditions.

Leaching of nitrate from agricultural land to groundwater and the resulting nitrate pollution are a major environmental problem worldwide. Its impact is often mitigated in aquifers hosting sufficiently reactive reductants that can promote autotrophic denitrification. In the case of pyrite acting as reductant, however, denitrification is associated with the release of sulfate and often also with the mobilization of trace metals (e.g., arsenic). In this study, reactive transport modeling was used to reconstruct, quantify and analyze the dynamics of the dominant biogeochemical processes in a nitrate-polluted pyrite-containing aquifer and its evolution over the last 50 years in response to changing agricultural practices. Model simulations were constrained by measured concentration depth profiles. Measured (3)H/(3)He profiles were used to support the calibration of flow and conservative transport processes, while the comparison of simulated and measured sulfur isotope signatures acted as additional calibration constraint for the reactive processes affecting sulfur cycling. The model illustrates that denitrification largely prevented an elevated discharge of nitrate to surface waters, while sulfate discharges were significantly increased, peaking around 15 years after the maximum nitrogen inputs.

Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.

Saline solutions are the most commonly used hydrological tracers, because they can be easily and economically monitored by in situ instrumentation such as electrical conductivity (EC) loggers in wells or by geoelectrical measurements. Unfortunately, these low-cost techniques only provide information on the total concentration of ions in solution, i.e., they cannot resolve the ionic composition of the aqueous solution. This limitation can introduce a bias in the estimation of aquifer parameters where sorption phenomena between saline tracers and sediments become relevant. In general, only selected anions such as Cl(-) and Br(-) are recognised to be transported unretarded and they are referred to as conservative tracers or mobile anions. However, cations within the saline tracer may interact with the soil matrix through a range of processes such as ion exchange, surface complexation and via physical mass-transfer phenomena. Heterogeneous reactions with minerals or mineral surfaces may not be negligible where aquifers are composed of fine alluvial sediments. The focus of the present study was to examine and to quantify the bias between the aquifer parameters estimated during model-based interpretation of experimental data of EC measurements of saline tracer relative to the aquifer parameters found by specific measurements (i.e. via ionic chromatography, IC) of truly conservative species. To accomplish this, column displacement experiments with alluvial aquifer materials collected from the Po lowlands (Italy) were performed under water saturated conditions. The behaviour of six selected, commonly used saline tracers (i.e., LiCl, KCl, and NaCl; LiBr, KBr, and NaBr) was studied and the data analysed by inverse modelling. The results demonstrate that the use of EC as a tracer can lead to an erroneous parameterisation of the investigated porous media, if the reactions between solute and matrix are neglected. In general, errors were significant except for KCl and KBr, which is due to the weak interaction between dissolved K(+) and the sediment material. The study shows that laboratory scale pre-investigations can help with tracer selection and to optimise the concentration range targeted for in situ multilevel monitoring by unspecific geoelectrical instrumentation., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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.

A model-based analysis of concentration and isotope data was carried out to assess natural attenuation of chlorinated ethenes in an aerobic fractured bedrock aquifer. Tetrachloroethene (PCE) concentrations decreased downgradient of the source, but constant delta13C signatures indicated the absence of PCE degradation. In contrast, geochemical and isotopic data demonstrated degradation of trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) under the prevailing oxic conditions. Numerical modeling was employed to simulate isotopic enrichment of chlorinated ethenes and to evaluate alternative degradation pathway scenarios. Existing field information on groundwater flow, solute transport, geochemistry, and delta13C signatures of the chlorinated ethenes was integrated via reactive transport simulations. The results provided strong evidence for the occurrence of aerobic TCE and DCE degradation. The chlorinated ethene concentrations together with stable carbon isotope data allowed us to reliably constrain the assessment of the extent of biodegradation at the site and plume simulations quantitatively linked aerobic biodegradation with isotope signatures in the field. Our investigation provides the first quantitative assessment of aerobic biodegradation of chlorinated ethenes in a fractured rock aquifer based on compound specific stable isotope measurements and reactive transport modeling.

The suitability of a granulated zero valent iron (ZVI) permeable reactive barrier (PRB) remediation strategy was investigated for tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE) and vinyl bromide (VB), via batch and large-scale column experiments that were subsequently analysed by reactive transport modelling. The brominated ethenes in both batch and large-scale column experiments showed rapid (compared to controls and natural attenuation) degradation in the presence of ZVI. In the large-scale column experiment, degradation half-lives were 0.35 days for TriBE, 0.50 days for c-DBE, 0.31 days for t-DBE and 0.40 days for VB, under site groundwater flow conditions, resulting in removal of brominated ethenes within the first 0.2 m of a 1.0 m thick ZVI layer, indicating that a PRB groundwater remediation strategy using ZVI could be used successfully. In the model simulations of the ZVI induced brominated ethene degradation, assuming a dominant reductive beta-elimination pathway via bromoacetylene and acetylene production, simulated organic compound concentrations corresponded well with both batch and large-scale column experimental data. Changes of inorganic reactants were also well captured by the simulations. The similar ZVI induced degradation pathway of TriBE and TCE suggests that outcomes from research on ZVI induced TCE remediation could also be applied to TriBE remediation.

Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.

Large-scale column experiments were carried out over a period of 545 days to assess the effect of increasing acidity on bacterial denitrification, sulfate reduction, and metal(loid) bioprecipitation in groundwater affected by acid mine drainage. At a groundwater pH of 5.5, denitrification and Cu2+ removal, probably via malachite (Cu2(OH)2CO3) precipitation, were observed in the ethanol-amended column. Sulfate reduction, sulfide production, and Zn2+ removal were also observed, with Zn2+ removal observed in the zone of sulfate reduction, indicating likely precipitation as sphalerite (ZnS). Se6+ removal was also observed in the sulfate reducing zone, probably as direct bioreduction to elemental selenium via ethanol/acetate oxidation or sulfide oxidation precipitating elemental sulfur. A step decrease in groundwater pH from 5.5 to 4.25 resulted in increased denitrification and sulfate reduction half-lives, migration of both these redox zones along the ethanol-amended column, and the formation of an elevated Cu2+ plume. Additionally, an elevated Zn2+ plume formed in the previous sulfate reducing zone of the ethanol-amended column, suggesting dissolution of precipitated sphalerite as a result of the reduction in groundwater pH. As Cu2+ passed through the zone of sphalerite dissolution, SEM imaging and EDS detection suggested that Cu2+ removal had occurred via chalcocite (Cu2S) or covellite (CuS) precipitation.

On the basis of a combination of laboratory microcosm experiments, column sorption experiments, and the current spatial distribution of groundwater concentrations, the origin of a mixed brominated ethene groundwater plume and its degradation pathway were hypothesized. The contaminant groundwater plume was detected downgradient of a former mineral processing facility, and consisted of tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE), and vinyl bromide (VB). The combined laboratory and field data provided strong evidence that the origin of the mixed brominated ethene plume was a result of dissolution of the dense non-aqueous-phase liquid 1,1,2,2-tetrabromoethane (TBA) atthe presumed source zone, which degraded rapidly (half-life of 0.2 days) to form TriBE in near stoichiometric amounts. TriBE then degraded (half-life of 96 days) to form c-DBE, t-DBE, and VB via a reductive debromination degradation pathway. Slow degradation of c-DBE (half-life >220 days), t-DBE (half-life 220 days), and VB (half-life >220 days) coupled with their low retardation coefficients (1.2, 1.2, and 1.0 respectively) resulted in the formation of an extensive mixed brominated ethene contaminant plume. Without this clearer understanding of the mechanism for TBA degradation, the origin of the mixed brominated ethene groundwater contamination could have been misinterpreted, and inappropriate and ineffective source zone and groundwater remediation techniques could be applied.

Reactive multicomponent transport modeling was used to investigate and quantify the factors that affect redox zonation and the fate of the pharmaceutical residue phenazone during artificial recharge of groundwater at an infiltration site in Berlin, Germany. The calibrated model and the corresponding sensitivity analysis demonstrated thattemporal and spatial redox zonation at the study site was driven by seasonally changing, temperature-dependent organic matter degradation rates. Breakthrough of phenazone at monitoring wells occurred primarily during the warmer summer months, when anaerobic conditions developed. Assuming a redox-sensitive phenazone degradation behavior the model results provided an excellent agreement between simulated and measured phenazone concentrations. Therefore, the fate of phenazone was shown to be indirectly controlled by the infiltration water temperature through its effect on the aquifer's redox conditions. Other factors such as variable residence times appeared to be of less importance.

Data obtained from a field study of an aquifer contaminated by landfill leachate and related laboratory experiments suggest that natural attenuation of phenoxy acid herbicides such as mecoprop (MCPP) occurs in the transition zone between the anaerobic plume core and the overlying aerobic water body. The location of this transition zone is assumed to be primarily controlled by vertical transverse dispersion processes occurring downstream of the pollution source. A reactive transport modeling study was carried out to evaluate this conceptual model. The transport was simulated for a two-dimensional vertical cross section to quantify the combined physical, geochemical, and microbial processes that affect the fate of the phenoxy acid herbicides. The simulations, showing removal of phenoxy acids, an increase of phenoxy acid degraders in the fringe zone, and a dependency of the results on vertical transverse dispersivity, are compatible with the hypothesis of fringe-controlled aerobic biodegradation of the phenoxy acids.