Model-Based Analysis of Arsenic Retention by Stimulated Iron Mineral Transformation under Coastal Aquifer Conditions.

A multitude of geochemical processes control the aqueous concentration and transport properties of trace metal contaminants such as arsenic (As) in groundwater environments. Effective As remediation, especially under reducing conditions, has remained a significant challenge. Fe(II) nitrate treatments are a promising option for As immobilization but require optimization to be most effective. Here, we develop a process-based numerical modeling framework to provide an in-depth understanding of the geochemical mechanisms controlling the response of As-contaminated sediments to Fe(II) nitrate treatment. The analyzed data sets included time series from two batch experiments (control vs treatment) and effluent concentrations from a flow-through column experiment. The reaction network incorporates a mixture of homogeneous and heterogeneous reactions affecting Fe redox chemistry. Modeling revealed that the precipitation of the Fe treatment caused a rapid pH decline, which then triggered multiple heterogeneous buffering processes. The model quantifies key processes for effective remediation, including the transfer of aqueous As to adsorbed As and the transformation of Fe minerals, which act as sorption hosts, from amorphous to more stable phases. The developed model provides the basis for predictions of the remedial benefits of Fe(II) nitrate treatments under varying geochemical and hydrogeological conditions, particularly in high-As coastal environments.

Sustaining Irrigation Supplies through Immobilization of Groundwater Arsenic In Situ.

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 m3 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 m2 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.

Process-Based and Probabilistic Quantification of Co and Ni Mobilization Risks Induced by Managed Aquifer Recharge.

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.

Molybdenum Mobility During Managed Aquifer Recharge in Carbonate Aquifers.

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.

Sulfate reduction accelerates groundwater arsenic contamination even in aquifers with abundant iron oxides.

Groundwater contamination by geogenic arsenic is a global problem affecting nearly 200 million people. In South and Southeast Asia, a cost-effective mitigation strategy is to use oxidized low-arsenic aquifers rather than reduced high-arsenic aquifers. Aquifers with abundant oxidized iron minerals are presumably safeguarded against immediate arsenic contamination, due to strong sorption of arsenic onto iron minerals. However, preferential pumping of low-arsenic aquifers can destabilize the boundaries between these aquifers, pulling high-arsenic water into low-arsenic aquifers. We investigate this scenario in a hybrid field-column experiment in Bangladesh where naturally high-arsenic groundwater is pumped through sediment cores from a low-arsenic aquifer, and detailed aqueous and solid-phase measurements are used to constrain reactive transport modelling. Here we show that elevated groundwater arsenic concentrations are induced by sulfate reduction and the predicted formation of highly mobile, poorly sorbing thioarsenic species. This process suggests that contamination of currently pristine aquifers with arsenic can occur up to over 1.5 times faster than previously thought, leading to a deterioration of urgently needed water resources.

Model-based identification of vadose zone controls on PFAS mobility under semi-arid climate conditions.

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.

Molybdenum Release Triggered by Dolomite Dissolution: Experimental Evidence and Conceptual Model.

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.

Sources of ammonium enriched in groundwater in the central Yangtze River Basin: Anthropogenic or geogenic?

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.

Noble gas constraints on the fate of arsenic in groundwater.

Groundwater contamination of geogenic arsenic (As) remains a global health threat, particularly in south-east Asia. The prominent correlation often observed between high As concentrations and methane (CH4) stimulated the analysis of the gas dynamics in an As contaminated aquifer, whereby noble and reactive gases were analysed. Results show a progressive depletion of atmospheric gases (Ar, Kr and N2) alongside highly increasing CH4, implying that a free gas phase comprised mainly of CH4 is formed within the aquifer. In contrast, Helium (He) concentrations are high within the CH4 (gas) producing zone, suggesting longer (groundwater) residence times. We hypothesized that the observed free (CH4) gas phase severely detracts local groundwater (flow) and significantly reduces water renewal within the gas producing zone. Results are in-line with this hypothesis, however, a second hypothesis has been developed, which focuses on the potential transport of He from an adjacent aquitard into the (CH4) gas producing zone. This second hypothesis was formulated as it resolves the particularly high He concentrations observed, and since external solute input from the overlying heterogeneous aquitard cannot be excluded. The proposed feedback between the gas phase and hydraulics provides a plausible explanation of the anti-intuitive correlation between high As and CH4, and the spatially highly patchy distribution of dissolved As concentrations in contaminated aquifers. Furthermore, the increased groundwater residence time would allow for the dissolution of more crystalline As-hosting iron(Fe)-oxide phases in conjunction with the formation of more stable secondary Fe minerals in the hydraulically-slowed (i.e., gas producing) zone; a subject which calls for further investigation.

In situ arsenic immobilisation for coastal aquifers using stimulated iron cycling: Lab-based viability assessment.

Arsenic (As) is one of the most harmful and widespread groundwater contaminants globally. Besides the occurrence of geogenic As pollution, there is also a large number of sites that have been polluted by anthropogenic activities, with many of those requiring active remediation to reduce their environmental impact. Cost-effective remedial strategies are however still sorely needed. At the laboratory-scale in situ formation of magnetite through the joint addition of nitrate and Fe(II) has shown to be a promising new technique. However, its applicability under a wider range of environmental conditions still needs to be assessed. Here we use sediment and groundwater from a severely polluted coastal aquifer and explore the efficiency of nitrate-Fe(II) treatments in mitigating dissolved As concentrations. In selected experiments >99% of dissolved As was removed, compared to unamended controls, and maintained upon addition of lactate, a labile organic carbon source. Pre- and post experimental characterisation of iron (Fe) mineral phases suggested a >90% loss of amorphous Fe oxides in favour of increased crystalline, recalcitrant oxide and sulfide phases. Magnetite formation did not occur via the nitrate-dependent oxidation of the amended Fe(II) as originally expected. Instead, magnetite is thought to have formed by the Fe(II)-catalysed transformation of pre-existing amorphous and crystalline Fe oxides. The extent of amorphous and crystalline Fe oxide transformation was then limited by the exhaustion of dissolved Fe(II). Elevated phosphate concentrations lowered the treatment efficacy indicating joint removal of phosphate is necessary for maximum impact. The remedial efficiency was not impacted by varying salinities, thus rendering the tested approach a viable remediation method for coastal aquifers.

Temperature dependence of nitrate-reducing Fe(II) oxidation by Acidovorax strain BoFeN1 - evaluating the role of enzymatic vs. abiotic Fe(II) oxidation by nitrite.

Fe(II) oxidation coupled to nitrate reduction is a widely observed metabolism. However, to what extent the observed Fe(II) oxidation is driven enzymatically or abiotically by metabolically produced nitrite remains puzzling. To distinguish between biotic and abiotic reactions, we cultivated the mixotrophic nitrate-reducing Fe(II)-oxidizing Acidovorax strain BoFeN1 over a wide range of temperatures and compared it to abiotic Fe(II) oxidation by nitrite at temperatures up to 60°C. The collected experimental data were subsequently analyzed through biogeochemical modeling. At 5°C, BoFeN1 cultures consumed acetate and reduced nitrate but did not significantly oxidize Fe(II). Abiotic Fe(II) oxidation by nitrite at different temperatures showed an Arrhenius-type behavior with an activation energy of 80±7 kJ/mol. Above 40°C, the kinetics of Fe(II) oxidation were abiotically driven, whereas at 30°C, where BoFeN1 can actively metabolize, the model-based interpretation strongly suggested that an enzymatic pathway was responsible for a large fraction (ca. 62%) of the oxidation. This result was reproduced even when no additional carbon source was present. Our results show that at below 30°C, i.e. at temperatures representing most natural environments, biological Fe(II) oxidation was largely responsible for overall Fe(II) oxidation, while abiotic Fe(II) oxidation by nitrite played a less important role.

Unraveling biogeochemical complexity through better integration of experiments and modeling.

The evolution of groundwater quality in natural and contaminated aquifers is affected by complex interactions between physical transport and biogeochemical reactions. Identifying and quantifying the processes that control the overall system behavior is the key driver for experimentation and monitoring. However, we argue that, in contrast to other disciplines in earth sciences, process-based computer models are currently vastly underutilized in the quest for understanding subsurface biogeochemistry. Such models provide an essential avenue for quantitatively testing hypothetical combinations of interacting, complex physical and chemical processes. If a particular conceptual model, and its numerical counterpart, cannot adequately reproduce observed experimental data, its underlying hypothesis must be rejected. This quantitative process of hypothesis testing and falsification is central to scientific discovery. We provide a perspective on how closer interactions between experimentalists and numerical modelers would enhance this scientific process, and discuss the potential limitations that are currently holding us back. We also propose a data-model nexus involving a greater use of numerical process-based models for a more rigorous analysis of experimental observations while also generating the basis for a systematic improvement in the design of future experiments.

Factors controlling iodine enrichment in a coastal plain aquifer in the North Jiangsu Yishusi Plain, China.

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 high­iodine 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.

Response of anaerobic granular sludge to long-term loading of roxarsone: From macro- to micro-scale perspective.

Extensive use of organoarsenic feed additives such as roxarsone has caused organoarsenicals to occur in livestock wastewater and further within anaerobic wastewater treatment systems. Currently, information on the long-term impacts of roxarsone on anaerobic granular sludge (AGS) activity and the underlying mechanisms is very limited. In this study, the response of AGS to long-term loading of roxarsone was investigated using a laboratory up-flow anaerobic sludge blanket reactor spiked with 5.0 mg L-1 of roxarsone. Under the effect of roxarsone, methane production decreased by ∼40% due to the complete inhibition on acetoclastic methanogenic activity on day 260, before being restored eventually. Over 30% of the influent arsenic was accumulated in the AGS and the capability of AGS to prevent intracellular As(III) accumulation increased with time. The AGS size was reduced by ∼30% to 1.20‒1.26 mm. Based on morphology and confocal laser scanning microscopy analysis, roxarsone exposure stimulated the excretion of extracellular polymeric substances and the surface spalling of AGS. High-throughput sequencing analysis further indicated roxarsone initially altered the acidogenic pathway and severely inhibited the acetoclastic methanogen Methanothrix. Acetogenic bacteria and Methanothrix were finally enriched and became the main contributor for a full restoration of the initial methane production. These findings provide a deeper understanding on the effect of organoarsenicals on AGS, which is highly beneficial for the effective anaerobic treatment of organoarsenic-bearing wastewater.

Carbon and methane cycling in arsenic-contaminated aquifers.

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 (δ13C-CH4, δ13C-DOC, δ13C-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 δ13C-CH4 from -87‰ to +47‰, indicating high reactivity. These findings demonstrate a previously overlooked role of methane cycling and DOC infiltration in high-As aquifers.

Fermentation, methanotrophy and methanogenesis influence sedimentary Fe and As dynamics in As-affected aquifers in Vietnam.

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 (CH4) 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 CH4 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.

Toward a more sustainable mining future with electrokinetic in situ leaching.

Metals are currently almost exclusively extracted from their ore via physical excavation. This energy-intensive process dictates that metal mining remains among the foremost CO2 emitters and mine waste is the single largest waste form by mass. We propose a new approach, electrokinetic in situ leaching (EK-ISL), and demonstrate its applicability for a Cu-bearing sulfidic porphyry ore. In laboratory-scale experiments, Cu recovery was rapid (up to 57 weight % after 94 days) despite low ore hydraulic conductivity (permeability = 6.1 mD; porosity = 10.6%). Multiphysics numerical model simulations confirm the feasibility of EK-ISL at the field scale. This new approach to mining is therefore poised to spearhead a new paradigm of metal recovery from currently inaccessible ore bodies with a markedly reduced environmental footprint.

Fluoride release from carbonate-rich fluorapatite during managed aquifer recharge: Model-based development of mitigation strategies.

Fluoride-bearing apatite minerals such as fluorapatite (FAP: Ca10(PO4)6F2) and related carbonate-rich fluorapatites (CFA: Ca10(PO4)5(CO3,F)F2), 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 CaCl2 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.

Mobilization of Arsenic and Other Naturally Occurring Contaminants during Managed Aquifer Recharge: A Critical Review.

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.

Enhancing Roxarsone Degradation and In Situ Arsenic Immobilization Using a Sulfate-Mediated Bioelectrochemical System.

Roxarsone (ROX) is widely used in animal farms, thereby producing organoarsenic-bearing manure/wastewater. ROX cannot be completely degraded and nor can its arsenical metabolites be effectively immobilized during anaerobic digestion, potentially causing arsenic contamination upon discharge to the environment. Herein, we designed and tested a sulfate-mediated bioelectrochemical system (BES) to enhance ROX degradation and in situ immobilization of the released inorganic arsenic. Using our BES (0.5 V voltage and 350 µM sulfate), ROX and its metabolite, 4-hydroxy-3-amino-phenylarsonic acid (HAPA), were completely degraded within 13-22 days. In contrast, the degradation efficiency of ROX and HAPA was <85% during 32-day anaerobic digestion. In a sulfate-mediated BES, 75.0-83.2% of the total arsenic was immobilized in the sludge, significantly more compared to the anaerobic digestion (34.1-57.3%). Our results demonstrate that the combination of sulfate amendment and voltage application exerted a synergetic effect on enhancing HAPA degradation and sulfide-driven arsenic precipitation. This finding was further verified using real swine wastewater. A double-cell BES experiment indicated that As(V) and sulfate were transported from the anode to the cathode chamber and coprecipitated as crystalline alacranite in the cathode chamber. These findings suggest that the sulfate-mediated BES is a promising technique for enhanced arsenic decontamination of organoarsenic-bearing manure/wastewater.