Reactive Solute Transport Model Research Articles

Prediction competitive multi-ions leaching under various flow chemistry conditions: Column studies and unified thermodynamic-kinetic modeling

Current models for inorganic ion transport in porous media describe the adsorption–desorption processes mostly based on empirical adsorption isotherms or simple thermodynamic mechanisms, often overlooking the adsorption kinetics. This study introduces a novel unified reactive solute transport model framework that incorporates well-established surface complexation models to describe the adsorption–desorption of ions in the transport process and takes into full consideration the non-equilibrium adsorption, enabling the use of the same set of thermodynamic-kinetic parameters to accurately describe ion transport under different chemical conditions. To evaluate the constructed model, Cr(VI), P(V), and As(V) column transport experiments were carried out using goethite-coated sand as the porous medium. Kinetic constants derived from single-ion transport experiments accurately predicted the cotransport behaviors of Cr(VI), P(V), and As(V) under various flow chemistry conditions, especially the overshooting phenomena of Cr(VI) under P(V) and As(V) competition. The model framework can be easily incorporated into solute transport models with various surface complexation reactions to predict the fate and transport of ions under complexed chemical conditions without extensive parameterization, and thus is a useful complement to the current reactive transport model.

Reactive Transport Modeling of Chemical Stimulation Processes for an Enhanced Geothermal System (EGS)

An enhanced geothermal system is a kind of artificial geothermal system, which can economically exploit geothermal energy from deep thermal rock mass with low permeability by artificially created geothermal reservoirs. Chemical stimulation refers to a reservoir permeability enhancement method that injects a chemical stimulant into the fractured geothermal reservoir to improve the formation permeability by dissolving minerals. In this study, a reactive solute transport model was established based on TOUGHREACT to find out the effect of chemical stimulation on the reconstruction of a granite-hosted enhanced geothermal system reservoir. The results show that chemical stimulation with mud acid as a stimulant can effectively improve the permeability of fractures near the injection well, the effective penetration distance can reach more than 20 m after 5 days. The improvement of porosity and permeability was mainly caused by the dissolution of feldspar and chlorite. The permeability enhancement increased with the injection flow rate and HF concentration in the stimulant, which was weakly affected by the change in injection temperature. The method of chemical enhancement processes can provide a reference for subsequent enhanced geothermal system engineering designs.

Field‐scale reactive transport assessment of CO2 storage in the Farnsworth unit through enhanced oil recovery practices

AbstractThe objective of this study was to investigate the transport and fate of CO2 injected into a sandstone reservoir in the western Farnsworth Unit, a hydrocarbon field in northern Texas. The study employed three‐dimensional multifluid‐phase numerical reactive solute and heat transport modeling. Model inputs were obtained from previous field characterization studies and calibrated to 8 years of historical production data. The CO2 in the models was injected through multiple wells for the first 25 years of the simulations according to a water‐alternating gas schedule. The simulations were carried out for a total of 1000 years in order to study the long‐term effects of CO2 injection.The results show that the largest fraction of the injected CO2 is stored in oil, followed by successively smaller amounts in the formation water, carbonate mineral phases, and as an immiscible gas phase. The small fraction of CO2 present as an immiscible gas, the most mobile phase for CO2, aids in the long‐term sequestration security of the injected CO2. The injected CO2 was found to migrate within a maximum radius of around 500 m of the injection wells. This means that changes in fluid pressure, temperature, composition, and reservoir mineralogy were also limited to occurring within this radius. This radius is very sensitive to model relative permeability and capillary pressure values, which were determined from history matching to the field production data. The models predicted dolomite to be the main mineral sink for the injected CO2. Quartz was another mineral predicted to precipitate, whereas calcite, albite, chlorite, illite, and kaolinite were predicted to dissolve. The changes in mineral abundance had minimal effect on porosity, implying that the permeability of the reservoir should also not change much because of CO2 injection. © 2023 Society of Chemical Industry and John Wiley & Sons, Ltd.

Modeling of dual-permeability gas and solute reactive transport in macroporous agricultural soils with a focus on GHG cycling and emissions

Agricultural soil is the domain where biogeochemical C-N turnover is affected by atmospheric and hydrologic processes, playing a vital role in anthropogenic greenhouse gas (GHG) emissions and thus affecting global climate change. GHG cycling and emissions are further complicated by the characteristics of soil structure, in particular macropores (i.e., preferential flow pathway). In this study, the processes of non-equilibrium gas diffusion and gas exchange were implemented into an existing dual-permeability flow and reactive solute transport model. The model was then used in a sensitivity analysis to evaluate the suitability of the modeling approach to account for development of anaerobic hotspots, with an emphasis on assessing N2O production and emissions. The sensitivity analysis combined with characteristic time scale analysis suggests that the development of anaerobic hotspots is controlled by a combination of both physical and geochemical parameters. Time scale analysis of O2 supply and consumption indicates that the occurrence of anaerobic hotspots is determined by the balance between characteristic times of O2 diffusion through the soil profile or exchange between macropores and the soil matrix, and the characteristic time of O2 consumption. Motivated by these findings, the present model was applied to simulate GHG cycling at a field site in Ontario, Canada, featuring macroporous agricultural soil. The model generally reproduced observed spatiotemporal variations in pore gas O2 and GHG concentrations and fluxes. Simulation results suggest that at this site, gas exchange processes between regions of preferential flow and the soil matrix play an important role in controlling the spatial variation of O2 in the soil. The simulations illustrate how the release of GHGs from the soil matrix into the macropores can lead to GHG emissions to the atmosphere. The modeling approach presented here, including dual domain flow and solute transport, as well as dual domain gas transport, shows promise for future studies with the aim to develop a more complete understanding of how soil structure affects complex GHG cycling in agricultural soils.

Effects of Water–Rock Interaction on the Permeability of the Near-Well Reservoir in an Enhanced Geothermal System

During the operation of an enhanced geothermal system (EGS), the non-equilibrium temperature, pressure, and hydrochemistry caused by fluid injection intensify water–rock interactions, induce the mineral dissolution and precipitation in the reservoir near an injection well (also referred to as the near-well reservoir), and change reservoir permeability, thus affecting continuous and efficient geothermal exploitation. Based on the investigation of the M-1 injection well of the EGS in the Matouying uplift of Hebei Province, China, a THC reactive solute transport model using the TOUGHREACT program was established in this study to explore the mineral dissolution and precipitation laws of the near-well reservoir and their influencing mechanisms on the reservoir porosity and permeability in the long-term fluid injection of this well. As indicated by the results, the dissolution of primary feldspar and chlorite and the precipitation of secondary minerals (mainly dolomite and illite) occurred and water–rock interaction significantly reduced the porosity and permeability of the near-well reservoir in the long-term continuous injection process. Appropriate reduction in the injection flow rate, injection temperature, and the Mg2+ and K+ contents in the injected water can help inhibit the formation of secondary minerals and delay the plugging process of the near-well reservoir.

Experiment and Simulation of Non-Reactive Solute Transport in Porous Media.

To more accurately predict the migration behavior of pollutants in porous media, we conduct laboratory scale experiments and model simulation. Aniline (AN) is used in one-dimensional soil column experiments designed under various media and hydrodynamic conditions. The advection-dispersion equation (ADE) and the continuous-time random walk (CTRW) were used to simulate the breakthrough curves (BTCs) of the solute transport. The results show that the media and hydrodynamic conditions are two important factors affecting solute transport and are related to the degree of non-Fickian transport. The simulation results show that CTRW can more effectively describe the non-Fickian phenomenon in the solute transport process than ADE. The sensitive parameter in the CTRW simulation process is , which can reflect the degree of non-Fickian diffusion in the solute transport. Understanding the relationship of with velocity and media particle size is conducive to improving the reactive solute transport model. The results of this study provide a theoretical basis for better prediction of pollutant transport in groundwater.

Bed form-induced hyporheic exchange and geochemical hotspots

Small-scale bed form topographies control hyporheic exchange and biogeochemical processes within aquatic sediments, which ultimately affect water quality and nutrient cycling at the watershed scale. The impact of three-dimensional and small-scale bed form topographies on hyporheic exchange and solute mixing is investigated in the present work. The effect of bed form morphologies on the development of zones of enhanced reaction rates (i.e., hotspots) is also studied. A computational fluid dynamics model to simulate river flow over bed forms is combined with a subsurface flow and multicomponent reactive solute transport model. A wide variety of bed form topographies are generated using geometric models by varying parameters controlling curvature as well as bed form wavelength and amplitude. The results in this research suggest that out-of-phase bed forms generate more complex hyporheic flow patterns which reduce the efficiency of solute transformations. Higher phase shifts in bed form shapes result in overall higher average velocity, larger zones of enhanced pressure and reaction rates, and higher amounts of solute exchange. Moreover, the bed form shapes control the reaction process for a wide range of sediment conductivities. This study advances the understanding of the effects of complex and small scale morphological features on hyporheic exchange processes including the rate and spatio-temporal distribution of reaction hotspots.

Modelling one-dimensional reactive transport of toxic contaminants in natural rivers

Solute transport models are widely employed to the predict spatio-temporal fate of contaminants in rivers. However, most previous studies have assumed that contaminants spilled are unreactive; they disregard the inherent reactivity of contaminants in water. The Reactive Solute Transport Model (RSTM) (Gooseff et al., 2005) includes lumped decay terms to reflect the decayability of the chemicals, but its applicability was still poor due to dependence on an optimization method. The purpose of this study is to perform reactive transport modelling considering chemicals’ reactivities for sorption, volatilization, and biodegradation. To this end, we manipulated the governing equations of the RSTM and suggested theoretical and empirical methods of estimating the key parameters of the reaction terms. The results showed, for example, that benzene lost 57.7% of its primary mass after being transported 4.54 km downstream due to its high volatility. Also, the arrival time of toluene was delayed by 10.4% due to adsorption.

Coupled Multifield Response to Coordinate Mining of Coal and Uranium: A Case Study

The coordinate mining of stack resources in the Ordos Basin, which involves the coupling effects of stress fracture, seepage, and reactive solute transport, plays an important role in resource exploration and environment protection. A coupled multiphysical–chemical model, involving a modified non-Darcy flow model, a leaching solution reaction, and a reactive solute transport model, was developed in this study. The Fast Lagrangian Analysis of Continua -Computational Fluid Dynamics (FLAC3D-CFD) simulator coupled with the developed models was used to investigate the evolution and morphology of mining-induced multifield coupling for the scenarios of concurrent mining and asynchronous mining of coal and uranium. As mining advanced to 160 m, the maximum principle stress characterized by a stress shell was observed. As mining progressed to 280 m, a rupture occurred, and a new stress shell was generated as a rear skewback was formed by the concentrated stress of the stope. An “arch-shaped” fracture field combined with a “saddle-shaped” seepage field was identified in the destressed zone of the stress shell. In the coordinated mining of uranium prior to coal, “funnel-shaped” and “asymmetric saddle-shaped” morphologies of the leaching solution were found during coal mining for ventilation in the stope and mining face. By contrast, “saddle-shaped”, “inclined funnel-shaped”, and “horizontal” morphologies of the leaching solution were observed for a short period for ventilation of the stope and mining face for coal mining prior to uranium mining, uranium mining prior to coal mining, and synchronized coal and uranium mining. A dynamic stress response was obtained in the coal seam, followed by the conglomerate aquifer and the uranium deposits. The diffusion depth of the solution was negatively correlated with the injection velocity and the pumping ratio and positively correlated with the diffusion coefficient. A dynamic increase in diffusion depth was observed as the diffusion coefficient increased to 1 × 10−4 m2/s.

Development of a groundwater flow and reactive solute transport model in the Yongding River alluvial fan, China

The Yongding River in the western suburbs of Beijing has been recharged with reclaimed water since 2010 for the purpose of ecological restoration. Where the reclaimed water is not well treated, it poses a danger to the aquifer underneath the river. To provide a reliable tool which could be used in future research to quantify the influence of reclaimed water in the Yongding River on the local groundwater environment, a transient groundwater flow and reactive solute transport model was developed using FEFLOW™ in the middle-upper part of the Yongding River Alluvium Fan. The numerical model was calibrated against the observed groundwater levels and the concentrations of typical solutes from June 2009 to May 2010 and validated from June 2010 to December 2010. The average RMSE and R2 of groundwater level at four observation wells are 0.48 m and 0.61, respectively. The reasonable agreement between observed and simulated results demonstrates that the developed model is reliable and capable of predicting the behavior of groundwater flow and typical contaminant transport with reactions. Water budget analysis indicates that the water storage in this aquifer had decreased by 43.76×106m3 from June 2009 to December 2010. The concentration distributions of typical solutes suggest that the middle and southern parts of the unconfined aquifer have been polluted by previous discharge of industrial and domestic sewage. The results underscore the necessity of predicting the groundwater response to reclaimed water being discharged into the Yongding River. The study established a coupled groundwater flow and reactive solute transport model in the middle-upper part of the Yongding River Alluvium Fan, one of the drinking water supply sites in Beijing city. The model would be used for risk assessment when reclaimed water was recharged into Yongding River.

Impacts of Yongding River Ecological Restoration on the Groundwater Environment: Scenario Prediction

Core Ideas Our method can estimate groundwater recharge through multiple contrasting lithological layers. Both human activities and natural aquifer character impact groundwater flow and transport. Geomembrane liners can effectively control the leakage from Yongding River. The ecological restoration of Yongding River can alleviate the local water deficit. Reclaimed water was discharged into the Yongding River channels as ecological water. Pollutants from such water may leak into the underlying aquifer and put the groundwater environment at risk. River leakage estimation under different possible river lining conditions and the established groundwater flow and reactive solute transport model were jointly applied to investigate the impact of the ecological restoration of the Yongding River on the local groundwater environment. Scenario‐based investigations were conducted since the channel reconstruction in 2009. The results show that the seepage from the Yongding River without liners can greatly raise the groundwater level. Leakage through liners constructed with geomembranes can effectively control the seepage of water and the spread of solutes in the aquifer. From June 2009 to December 2010, the leakage amount has been only 1.65 × 104 m3, and the unconfined aquifer shows a negative budget of 4.55 × 107 m3. The spreading extent of flow and potential pollutants increases with the amount of leakage from the river. Water management strategies, such as the South‐to‐North Water Diversion Project and Yongding River restoration could help alleviate the water deficit of the Yongding River alluvium fan (YRAF) by reducing groundwater exploitation and increasing groundwater recharge. The necessity of the maintenance of riverbed liners and control of the water quality of Yongding River were highlighted by the scenario analysis. The methods applied in this study could be used for reference in the other polluted rivers, especially with liner installation.

Influence of multi-species solute transport on modeling of hydrated Portland cement leaching in strong nitrate solutions

The differences between the predictions of Fickian diffusion and Nernst-Planck electro-diffusion based reactive transport models are investigated in the context of an important practical problem – leaching of Portland cement in strong nitrate porewater solutions under saturated conditions. Numerical results are presented for three distinct porewater solutions: deionized water, ammonium nitrate solution, and diluted porewater from a cementitious low-activity nuclear waste form. Solute concentrations predicted by the two transport models show significant differences: as much as a factor of two for ammonium nitrate leaching and as much as a factor of four for waste form leaching; whereas, negligible differences are observed for deionized water leaching. The major conclusion is that Fickian diffusion may be accurate enough for deionized water leaching, but electro-diffusion should be considered in the reactive solute transport modeling of ammonium nitrate decalcification and in the degradation modeling of cementitious materials exposed to nuclear waste form solutions.

Use of a Three-Dimensional Reactive Solute Transport Model for Evaluation of Bioreactor Placement in Stream Restoration.

A three-dimensional groundwater flow and multispecies reactive transport model was used to strategically design placement of bioreactors in the subsurface to achieve maximum removal of nitrate along restored stream reaches. Two hypothetical stream restoration scenarios were evaluated over stream reaches of 40 and 94 m: a step-pool scenario and a channel re-meandering scenario. For the step-pool scenario, bioreactors were placed at locations where mass fluxes of groundwater and nitrate were highest. Bioreactors installed over 50% of the total channel length of a step-pool scenario (located to intercept maximum groundwater and nitrate mass flux) removed nitrate-N entering the channel at a rate of 36.5 kg N yr (100 g N d), achieving about 65% of the removal of a whole-length bioreactor. Bioreactor placement for the re-meandering scenario was designed using a criterion of either highest nitrate mass flux or highest groundwater flux, but not both, because they did not occur together. Bioreactors installed at maximum nitrate flux locations (53% of the total channel length) on the western bank removed nitrate-N entering the channel at 62.0 kg N yr (170 g N d), achieving 85% of nitrate-N removal of whole-length bioreactors for the re-meandering scenario. Bioreactors installed at maximum groundwater flux locations on the western bank along approximately 40% of the re-meandering channel achieved about 65% of nitrate removal of whole-length bioreactors. Placing bioreactors at maximum nitrate flux locations improved denitrification efficiency. Due to low groundwater velocities, bioreactor nitrate-N removal was found to be nitrate limited for all scenarios.

Modeling and analysis of reactive solute transport in deformable channels with wall adsorption–desorption

We show well posedness for a model of nonlinear reactive transport of chemical in a deformable channel. The channel walls deform due to fluid–structure interaction between an unsteady flow of an incompressible, viscous fluid inside the channel and elastic channel walls. Chemical solutes, which are dissolved in the viscous, incompressible fluid, satisfy a convection–diffusion equation in the bulk fluid, while on the deforming walls, the solutes undergo nonlinear adsorption–desorption physico‐chemical reactions. The problem addresses scenarios that arise, for example, in studies of drug transport in blood vessels. We show the existence of a unique weak solution with solute concentrations that are non‐negative for all times. The analysis of the problem is carried out in the context of semi‐linear parabolic PDEs on moving domains. The arbitrary Lagrangian–Eulerian approach is used to address the domain movement, and the Galerkin method with the Picard–Lindelöf theorem is used to prove existence and uniqueness of approximate solutions. Energy estimates combined with the compactness arguments based on the Aubin–Lions lemma are used to prove convergence of the approximating sequences to the unique weak solution of the problem. It is shown that the solution satisfies the positivity property, that is, that the density of the solute remains non‐negative at all times, as long as the prescribed fluid domain motion is ‘reasonable’. This is the first well‐posedness result for reactive transport problems defined on moving domains of this type. Copyright © 2015 John Wiley & Sons, Ltd.

Numerical modeling of reactive solute transport in a single fracture with matrix diffusion under complex boundary condition

A numerical model using finite volume QUICK scheme has been developed for simulating the transport behavior of solutes in a coupled fracture–matrix system for pulse-type boundary condition as against the conventional constant continuous source-type boundary condition, which essentially reflects the reality better, as it is practically not feasible for any source type to discharge it continuously with the same magnitude for a very long period. The sensitivity of fracture and rock matrix parameters, namely fracture aperture thickness, matrix porosity, and matrix diffusion coefficient have been analyzed under this complex boundary condition. In addition, the role of nonlinear sorption as well as decay has also been investigated. Numerical results suggest that the reduction in relative concentration within the fracture resulting from pulse-type boundary condition should always not be mistaken for matrix diffusion. It has been concluded from the present numerical study that segregating and quantifying the role on individual components, namely (a) source exhaustion (pulse-type boundary condition); (b) matrix diffusion; (c) sorption; and (d) decay in characterizing the resultant transport behavior of solutes in a single fracture with matrix diffusion under a pulse-type boundary condition remains challenging and needs further research.

Groundwater flow dynamics and arsenic source characterization in an aquifer system of West Bengal, India

AbstractNumerical groundwater flow modeling, reverse particle tracking, and environmental tracers are used to locate the source of geogenic As affecting an aquifer in West Bengal. The aquifer is hosted by point‐bar sands deposited in a meandering fluvial environment. Wells tapping the aquifer exhibit As concentrations up to 531 μg/L. High‐As groundwaters are recharged in ponds marking an abandoned river channel. The source of As is traced to the underlying fine‐grained channel‐fill sediments. Arsenic release within these sediments is accompanied by a concomitant release of Br and DOC indicating that these species may be decay products of natural organobromines codeposited along with As. Mass transfer of As to the dissolved phase and its flushing from source sediments are described using a simplified reactive solute transport model. Based on this model, a characteristic reaction time for mass transfer is estimated at 6.7 years. Average groundwater residence times in the source are estimated to have declined from 16.6 to 6.6 years with the advent of intensive irrigation pumping. The ratio of residence and reaction times, a Damköhler number, has declined correspondingly from 2.49 to 0.99, indicating a shift from transport to reaction rate limited As mobilization. Greater insight into the As problem in SE Asia may be achieved by shifting the focus of field investigations from aquifers to potential contamination sources in aquitards.

PoreFlow: A complex pore-network model for simulation of reactive transport in variably saturated porous media

This study introduces PoreFlow, a pore-network modeling tool capable of simulating fluid flow and multi-component reactive and adsorptive transport under saturated and variably saturated conditions. PoreFlow includes a variety of modules, such as: pore network generator, drainage simulator, calculation of pressure and velocity distributions, and modeling of reactive solute transport accounting for advection and diffusion. The pore space is represented using a multi-directional pore-network capable of capturing the random structure of a given porous media with user-defined directional connectivities for anisotropic pore structures. The chemical reactions can occur within the liquid phase, as well as between the liquid and solid phases which may result in an evolution of porosity and permeability. Under variably saturated conditions the area of interfaces changes with degree of the fluid saturation.PoreFlow uses complex formulations for more accurate modeling of transport problems in presence of the nonwetting phase. This is done by refining the discretization within drained pores. An implicit numerical scheme is used to solve the governing equations, and an efficient substitution method is applied to considerably minimize computational times. Several examples are provided, under saturated and variably saturated conditions, to demonstrate the model applicability in hydrogeology problems and petroleum fields. We show that PoreFlow is a powerful tool for upscaling of flow and transport in porous media, utilizing different pore scale information such as various interfaces, phase distributions and local fluxes and concentrations to determine macro scale properties such as average saturation, relative permeability, solute dispersivity, adsorption coefficients, effective diffusion and tortuosity. Such information can be used as constitutive relations within continuum scale governing equations to model physical and chemical processes more accurately at the larger scales.

Aquifer geochemistry at potential aquifer storage and recovery sites in coastal plain aquifers in the New York city area, USA

Abstract The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water. The simulated injection of buffered, oxic city water into a hypothetical ASR well increased the hydraulic head at the well, displaced the ambient groundwater, and formed a spheroid of injected water with lower concentrations of Fe, Mn and major ions in water surrounding the ASR well, than in ambient water. Both the dissolved O 2 concentrations and the pH of water near the well generally increased in magnitude during the simulated 5-a injection phase. The resultant oxidation of Fe 2+ and attendant precipitation of goethite during injection provided a substrate for sorption of dissolved Fe during the 8-a extraction phase. The baseline scenario with a low (0.001 M) concentration of pyrite in aquifer sediments, indicated that nearly 190% more water with acceptably low concentrations of dissolved Fe could be extracted than was injected. Scenarios with larger amounts of pyrite in aquifer sediments generally resulted in less goethite precipitation, increased acidity, and increased concentrations of dissolved Fe in extracted water. In these pyritic scenarios, the lower amounts of goethite precipitated and the lower pH during the extraction phase resulted in decreased sorption of Fe 2+ and a decreased amount of extractable water with acceptably low concentrations of dissolved Fe (5.4 × 10 −6 M). A linear decrease in recovery efficiency with respect to dissolved Fe concentrations is caused by pyrite dissolution and the associated depletion of dissolved O 2 (DO) and increase in acidity. Simulations with more than 0.0037 M of pyrite, which is the maximum amount dissolved in the baseline scenario, had just over a 50% recovery efficiency. The precipitation of ferric hydroxide minerals (goethite) at the well screen, and a possible associated decrease in specific capacity of the ASR well, was not apparent during the extraction phase of ASR simulations, but the model does not incorporate the microbial effects and biofouling associated with ferric hydroxide precipitation. The host groundwater chemistry in calcite-poor Cretaceous aquifers of the NYC area consists of low alkalinity and moderate to low pH. The dissolution of goethite in scenarios with unbuffered injectate indicates that corrosion of the well could occur if the injectate is not buffered. Simulations with buffered injectate resulted in greater precipitation of goethite, and lower concentrations of dissolved Fe, in the extracted water. Dissolved Fe concentrations in extracted water were highest in simulations of aquifers (1) in which pyrite and siderite in the aquifer were in equilibrium, and (2) in coastal areas affected by saltwater intrusion, where high dissolved-cation concentrations provide a greater exchange of Fe 2+ (FeX 2 ). Results indicate that ASR in pyrite-bearing, Cretaceous aquifers of the NYC area can be a cost effective way to both store drinking water supplies and significantly reduce ambient concentrations of dissolved Fe.

A coupled THMC model of a heating and hydration laboratory experiment in unsaturated compacted FEBEX bentonite

Summary Unsaturated compacted bentonite is foreseen by several countries as a backfill and sealing material in high-level radioactive waste repositories. The strong interplays between thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes during the hydration stage of a repository call for fully coupled THMC models. Validation of such THMC models is prevented by the lack of comprehensive THMC experiments and the difficulties of experimental methods to measure accurately the chemical composition of bentonite porewater. We present here a non-isothermal multiphase flow and multicomponent reactive solute transport model for a deformable medium of a heating and hydration experiment performed on a sample of compacted FEBEX bentonite. Besides standard solute transport and geochemical processes, the model accounts for solute cross diffusion and thermal and chemical osmosis. Bentonite swelling is solved with a state-surface approach. The THM model is calibrated with transient temperature, water content and porosity data measured at the end of the experiment. The reactive transport model is calibrated with porewater chemical data derived from aqueous extract data. Model results confirm that thermal osmosis is relevant for the hydration of FEBEX bentonite while chemical osmosis can be safely neglected. Dilution and evaporation are the main processes controlling the concentration of conservative species. Dissolved cations are mostly affected by calcite dissolution–precipitation and cation exchange reactions. Dissolved sulphate is controlled by gypsum/anhydrite dissolution–precipitation. pH is mostly buffered by protonation/deprotonation via surface complexation. Computed concentrations agree well with inferred aqueous extract data at all sections except near the hydration boundary where cation data are affected by a sampling artifact. The fit of Cl− data is excellent except for the data near the heater. The largest deviations of the model from inferred aqueous extract data occur for dissolved SO 4 2 - which is underpredicted by the model. There are uncertainties on the amount of gypsum available for dissolution and its dissolution mechanism (kinetics or local equilibrium).

On the relevance of electrochemical diffusion for the modeling of degradation of cementitious materials

Abstract Reactive solute transport models have been broadly used over the last years to evaluate the durability of cementitious materials because they provide a mechanistic approach to cope with the complex diffusion–reaction phenomena involved in cement and concrete degradation processes. However, most of the numerical models published in the scientific literature use Fick’s law as the constitutive equation for the diffusive transport of dissolved ions, neglecting the electrochemical constraints imposed by the various ionic fluxes, which conspire against the local electroneutrality of the system. In this work, the relevance of electrochemical diffusion and its impact on the nonlinear coupled phenomena concerned by cement degradation were evaluated, on the basis of its influence on the simulation of deterioration of concrete exposed to weak sulfate solutions. Results obtained show that diffusive approaches based on Fick’s law may not be accurate enough for modeling the degradation of cementitious materials since, for the case considered, when ignored, electrochemical interactions in the diffusion process may lead to the inability of reactive transport models to reproduce key phenomena such as gypsum precipitation near the exposed cement surface.