RESUMO
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.
Assuntos
Água Subterrânea , Níquel , Poluentes Químicos da Água , Água Subterrânea/química , CobaltoRESUMO
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.
Assuntos
Irrigação Agrícola , Arsênio , Água Subterrânea , Poluentes Químicos da Água , Água Subterrânea/química , Poluentes Químicos da Água/química , Ferro/química , NitratosRESUMO
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.
Assuntos
Água Subterrânea , Poluentes Químicos da Água , Fluoretos , Minerais , FosfatosRESUMO
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.
Assuntos
Arsênio , Água Subterrânea , Poluentes Químicos da Água , Purificação da Água , SulfetosRESUMO
Recent laboratory studies have demonstrated that coinjection of nitrate and Fe(II) (as ferrous sulfate) to As-bearing sediments can produce an Fe mineral assemblage containing magnetite capable of immobilizing advected As under a relatively wide range of aquifer conditions. This study combined laboratory findings with process-based numerical modeling approaches, to quantify the observed Fe mineral (trans)formation and concomitant As partitioning dynamics and to assess potential nitrate-Fe(II) remediation strategies for field implementation. The model development was guided by detailed solution and sediment data from our well-controlled column experiment. The modeling results demonstrated that the fate of As during the experiment was primarily driven by ferrihydrite formation and reductive transformation and that different site densities were identified for natural and neoformed ferrihydrite to explain the observations both before and after nitrate-Fe(II) injection. Our results also highlighted that when ferrihydrite was nearing depletion, As immobilization ultimately relied on the presence of magnetite. On the basis of the column model, field-scale predictive simulations were conducted to illustrate the feasibility of the nitrate-Fe(II) strategy for intercepting advected As from a plume. The predictive simulations, which suggested that long-term As immobilization was feasible, favored a scenario that maintains high dissolved Fe(II) concentration during injection periods and thereby converts ferrihydrite to magnetite.
Assuntos
Arsênio , Água Subterrânea , Compostos Férricos , Óxido Ferroso-Férrico , Ferro , Minerais , OxirreduçãoRESUMO
Microbially driven nitrate-dependent iron (Fe) oxidation (NDFO) in subsurface environments has been intensively studied. However, the extent to which Fe(II) oxidation is biologically catalyzed remains unclear because no neutrophilic iron-oxidizing and nitrate reducing autotroph has been isolated to confirm the existence of an enzymatic pathway. While mixotrophic NDFO bacteria have been isolated, understanding the process is complicated by simultaneous abiotic oxidation due to nitrite produced during denitrification. In this study, the relative contributions of biotic and abiotic processes during NDFO were quantified through the compilation and model-based interpretation of previously published experimental data. The kinetics of chemical denitrification by Fe(II) (chemodenitrification) were assessed, and compelling evidence was found for the importance of organic ligands, specifically exopolymeric substances secreted by bacteria, in enhancing abiotic oxidation of Fe(II). However, nitrite alone could not explain the observed magnitude of Fe(II) oxidation, with 60-75% of overall Fe(II) oxidation attributed to an enzymatic pathway for investigated strains: Acidovorax ( A.) strain BoFeN1, 2AN, A. ebreus strain TPSY, Paracoccus denitrificans Pd 1222, and Pseudogulbenkiania sp. strain 2002. By rigorously quantifying the intermediate processes, this study eliminated the potential for abiotic Fe(II) oxidation to be exclusively responsible for NDFO and verified the key contribution from an additional, biological Fe(II) oxidation process catalyzed by NDFO bacteria.
Assuntos
Compostos Ferrosos , Ferro , Nitratos , Nitritos , OxirreduçãoRESUMO
Faults can fundamentally change a groundwater flow regime and represent a major source of uncertainty in groundwater studies. Much research has been devoted to uncertainty around their location and their barrier-conduit behavior. However, fault timing is one aspect of fault uncertainty that appears to be somewhat overlooked. Many faulted models feature consistent layer offsets, thereby presuming that block faulting has occurred recently and almost instantaneously. Additionally, barrier and/or conduit behavior is often shown to extend vertically through all layers when a fault may in fact terminate well below-ground surface. In this study, we create three plausible geological interpretations for a transect in the Perth Basin. Adjacent boreholes show stratigraphic offsets and thickening which indicate faulting; however, fault timing is unknown. Flow modeling demonstrates that the model with the most recent faulting shows profoundly different flow patterns due to aquifer juxtaposition. Additionally, multiple realizations with stochastically generated parameter sets for layer, fault core, and fault damage zone conductivity show that fault timing influences flow more than layer or fault zone conductivity. Finally, fault conduit behavior that penetrates aquitards has significant implications for transport, while fault barrier behavior has surprisingly little. This research advocates for adequate data collection where faults may cause breaches in aquitards due to layer offsets or conduit behavior in the damage zone. It also promotes the use of multiple geological models to address structural uncertainty, and highlights some of the hurdles in doing so such as computational expense and the availability of seamless geological-flow modeling workflows.
RESUMO
Sedimentary structures have unique geometries and anisotropic hydraulic conductivity, both of which control groundwater flow. Traditional finite-difference simulators (e.g., MODFLOW) have not been able to correctly represent irregular, dipping and anisotropic structures due their use of a simplified conductivity tensor, causing many modelers to turn toward finite-element codes with their sophisticated meshing capabilities. However, the release of MODFLOW 6 with its flexible discretization and multipoint flux approximation scheme prompts us to revisit its capability to compute flow through complex sedimentary structures. Through the use of a novel benchmark and case study, we show that when versions previous to MODFLOW 6 are applied to dipping structures, modeled fluxes and hence flow through the system, can be significantly over or underestimated. For example, effective conductivity for a 30° dipping layer with a 100:1 conductivity ratio is reduced to only 2% of its inputted value. We show that MODFLOW 6, with its XT3D capability and flexible discretization options is far superior to its predecessors, allowing flow through complex sedimentary structures to be simulated more accurately. However, on vertically offset grids, which have been available in all versions of MODFLOW and are often used in practice, loss of accuracy is still a concern when the vertical offset is large, that is, the dip of the sedimentary layer is steep, particularly if the layer is much more conductive than the surrounding material. The hypothesis that vertically offset grids lack sufficient hydraulic connectivity between adjacent model layers to accurately simulate the steeply dipping, highly heterogeneous case is a topic for further investigation.
RESUMO
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.
Assuntos
Água Subterrânea , Simulação por Computador , Modelos TeóricosRESUMO
Numerous experimental studies have identified a multi-step reaction mechanism to control arsenite (As(III)) oxidation by manganese (Mn) oxides. The studies highlighted the importance of edge sites and intermediate processes, e.g., surface passivation by reaction products. However, the identified reaction mechanism and controlling factors have rarely been evaluated in a quantitative context. In this study, a process-based modeling framework was developed to delineate and quantify the relative contributions and rates of the different processes affecting As(III) oxidation by Mn oxides. The model development and parameterization were constrained by experimental observations from literature studies involving environmentally relevant Mn oxides at circumneutral pH using both batch and stirred-flow reactors. Our modeling results highlight the importance of a transitional phase, solely evident in the stirred-flow experiments, where As(III) oxidation gradually shifts from fast reacting Mn(IV) to slowly reacting Mn(III) edge sites. The relative abundance of these edge sites was the most important factor controlling the oxidation rate, whereas surface passivation restricted oxidation only in the stirred-flow experiment. The Mn(III) edge sites were demonstrated to play a crucial role in the oxidation and therefore in controlling the long-term fate of As. This study provided an improved understanding of Mn oxide reactivity and the significance in the cycling of redox-sensitive metal(loid)s in the environment.