Multi-species Reactive Transport Model Research Articles

A multi-species reactive transport model based on gas-ion-solid phase interaction for the carbonation of cement-based materials

This study presents a reactive transport modelling framework for understanding carbonation processes through pore solution composition, phase assemblage changes in cement-based materials, and pore solution composition changes on steel corrosion. The study emphasizes the significance of considering pore structure changes on mass transport and utilizing a surface complexation model for predicting changes in pore solution composition and comprehending its influence on steel corrosion. A clear enrichment in sodium and potassium content in carbonated regions is observed upon carbonation, which leads to a decrease in alkali concentration in the pore solution, and alkali ions are transported toward the carbonated zone. Simultaneously, the opposite behaviour is observed for both the sulphur and chloride content. The increase in the concentration of sulphur and chloride in the pore solution was observed upon the decomposition of the solid phase. Calcium ions are transported to the carbonated zone, further increasing calcite formation near the exposed surface.

A coupled flow and transport model for simulation of multi-species reactive transport in unconfined aquifer using meshless local Petrov Galerkin (MLPG) method.

An understanding of natural degradation of multiple reactive contaminants in the aquifers is essential before designing the monitoring or remediation programs for polluted aquifers. Since such reactive contaminants are ubiquitous, a number of research works has been performed in the past three decades for the modelling of multi-species reactive transport (MSRT) phenomenon. The widely used finite difference method (FDM) and finite element method (FEM)-based models suffer a drawback of relying on a grid/mesh, which makes the solution unstable. Addressing such difficulties, the latest research on the MSRT models is directed towards the meshless methods. In this study, the meshless local Petrov Galerkin (MLPG) method-based multi-species reactive transport model (MLPG-MSRT) is presented, with an objective to create a robust simulation tool for the prediction of fate of multiple contaminants of the first-order reaction network. The developed model is validated for reversible as well as irreversible reaction networks with the available analytical solutions. Also, the MLPG model for unconfined aquifer flow (UF) is developed, validated, and coupled with the MLPG-MSRT model. The MLPG-UF-MSRT model results are further compared with the established FDM-based MODFLOW-RT3D model solutions for a rectangular and a real field type study. The results showed that the proposed model can simulate MSRT as accurately as the FDM-based models with an additional advantage of simplicity and stability, and thus, is more efficient for complex field problems.

Enhancement of a multi-species reactive transport model for cement-based materials under cyclic wetting and drying conditions

To understand the underlying phenomena that drive concrete deterioration under cyclic environmental conditions in the marine environment, a reactive transport model (RTM) for unsaturated cement-based materials has been established in this study, including multi-ionic and moisture transport coupled with a chemical equilibrium computation. The two-phase moisture transport model, which considers pore structure changes, is introduced with capillary pressure as the primary variable parameter. The modified Poisson-Nernst-Planck (PNP) equations were illustrated for multi-ionic transport through pore solution under unsaturated conditions. A modelling approach for moisture conductivity based on the pore structure and moisture storage was presented to account for pore structure changes on the mass transports. The consideration of boundary conditions and moisture flux through the exposed surface is demonstrated for wetting and drying conditions, separately. Numerical results for mortar samples subjected to NaCl solutions under various cyclic wetting and drying conditions were in good agreement with experimentally measured moisture gain and total chloride content. Under more prolonged wetting conditions, the deeper influence depth and a wider range of moisture fluctuation lead to an increase in concrete deterioration. For all cyclic wetting conditions, the precipitation of Friedel's salt is predicted, which subsequently limits the transport of chloride ions to deeper depths from the exposed surface. A peak in the chloride profile is observed near the exposed surface. Meanwhile, the peak region continuously expands and moves deeper into the specimens with increasing wetting time duration and exposure times, consistent with Friedel's salt precipitation. In contrast, the chloride content near the exposure surface shows a significant decrease due to the decomposition of the C–S–H phase caused by ion leaching and carbonation of the exposed surface.

A multi-species reactive transport model based on ion-solid phase interaction for saturated cement-based materials

This study established a reactive transport model (RTM) for saturated cement-based materials based on multi-ionic transport through an uncharged, ‘free water’ and charged, ‘the electrical double layer’ coupled with a chemical equilibrium model for interaction between pore solution and solid phase. A set of modified Poisson-Nernst-Planck equations, including the effect of temperature, pore solution property, and pore structure changes, have been introduced for multi-ionic transport. A comprehensive method has been illustrated for determining the diffusion coefficient at infinite dilution of the aqueous species present in the pore solution in a cementitious material. Numerical predictions were compared to experimental data to demonstrate the applicability of the RTM. For mortar specimens exposed to NaCl solution and seawater, numerical predictions agree well with experimentally determined Portlandite and carbonate in the phase assemblage, elemental distribution such as chloride, sodium, potassium, magnesium, and sulfur adjusting the initial tortuosity factor.

An Enhancement of a Multi-Species Reactive Transport Model for Cement-Based Materials Under Dry and Wet Conditions

An Enhancement of a Multi-Species Reactive Transport Model for Cement-Based Materials Under Dry and Wet Conditions

Modeling the Formation and Propagation of 2,4,6-trichloroanisole, a Dominant Taste and Odor Compound, in Water Distribution Systems

2,4,6-trichloroanisole (2,4,6-TCA) formation is often reported as a cause of taste and odor (T&O) problems in water distribution systems (WDSs). The biosynthesis via microbial O-methylation of 2,4,6-trichlorophenol (2,4,6-TCP) is the dominant formation pathway in distribution pipes. This paper attempted to utilize the reported data on the microbial O-methylation process to formulate deterministic kinetic models for explaining 2,4,6-TCA formation dynamics in WDSs. The pipe material’s critical role in stimulating O-methyltransferases enzymatic activity and regulating 2,4,6-TCP bioconversion in water was established. The kinetic expressions formulated were later applied to develop a novel EPANET-MSX-based multi-species reactive-transport (MSRT) model. The effects of operating conditions and temperature in directing the microbiological, chemical, and organoleptic quality variations in WDSs were analyzed using the MSRT model on two benchmark systems. The simulation results specified chlorine application’s implication in maintaining 2,4,6-TCA levels within its perception limit (4 ng/L). In addition, the temperature sensitivity of O-methyltransferases enzymatic activity was described, and the effect of temperature increase from 10 to 25 °C in accelerating the 2,4,6-TCA formation rate in WDSs was explained. Controlling source water 2,4,6-TCP concentration by accepting appropriate treatment techniques was recommended as the primary strategy for regulating the T&O problems in WDSs.

Numerical investigation of critical electrochemical factors for pitting corrosion using a multi-species reactive transport model

A multi-species reactive transport model based on the sequential non-iterative approach is employed to investigate two major stages involved in artificial pit experiments of stainless steel: I. Stable dissolution under a salt film and II. Film-free dissolution that transitions to repassivation. Data of current density and electrical potential obtained from rapid polarization scans of pits with different depths are utilized to calibrate the elapsed time and the electrode kinetics of each stage. The local chemistry near the base of pits at different temperature and bulk concentrations is simulated to determine several critical electrochemical factors at saturation and repassivation.

Numerical Modeling on the Influence of Effective Porosity, Microbial Kinetics, and Operational Parameters on Enhanced Oil Recovery by Microbial Flooding Within a Sandstone Formation

Summary During the implementation of a microbial-enhanced-oil-recovery (EOR) (MEOR) technique in a sandstone formation, various reservoir physicochemical, microbial kinetic, and operational parameters play major roles in governing the efficiency of crude-oil recovery from a hydrocarbon reservoir. The present study numerically investigates the sensitivity of sandstone formation effective porosity; different injected strains of the species Bacillus under optimal metabolic conditions and possessing distinct values of maximum microbial-specific-growth rate, Monod saturation constant, and yield coefficient; and crucial operational parameters on biomass and biosurfactant production and their effects on microscopic oil-displacement efficiency within the sandstone reservoir, along with prompting modifications in rock physicochemical properties. A black-oil biochemical multispecies reactive transport model in porous sandstone media is developed by coupling the kinetic model with the corresponding transport model involving microbial sorption. The governing equations involve coupled transport of nutrients and microbes by dispersion and convection, growth and decay rates of microbes, chemotaxis, nutrient consumption, and deposition of microbes and nutrients on rock-grain surfaces caused by reversible/irreversible sorption. Coupled empirical equations are used to estimate biosurfactant production, oil/water-interfacial-tension (IFT) reduction, change in the viscosity of injection fluid, and their effects on oil relative permeability and mobility, and thus a decrease in residual oil saturation within the reservoir. The finite-difference-discretization technique is adopted to solve the governing equations. Results of the present model are found to be numerically stable and match very well, when verified, with the previously published analytical, numerical, and experimental results. The model results suggest that at very low reservoir porosity (approximately 10%), an early breakthrough of nutrients, microbes, and biosurfactant leave insignificant concentrations in their respective fronts, which are insufficient for the recovery of the trapped oil. Also, increase in porosity to approximately 30% and beyond causes loss of nutrients, microbes, and biosurfactant because they undergo higher dispersion during their transport within the reservoir. Thus, sandstone formations possessing an intermediate effective porosity value of approximately 20% significantly enhance the efficiency of the overall MEOR process. Further, it is observed that the nature of microbes and nutrients used for MEOR application affect biosurfactant production, and in turn oil recovery, to a large extent. Those microbial species with far lower Monod-saturation-constant values have high affinity toward their substrates. This phenomenon dramatically increases the rates of nutrient consumption and production of biomass and biosurfactant within a reservoir when suitable substrate compounds are used, irrespective of differences in the yield coefficients of the microbes. Further MEOR simulation studies within a sandstone core exhibited maximum oil displacement and recovery at a run time of 5 hours, injected-microbial concentration of 4.32×10–3 mg/cm3, and maximum specific growth rate of 0.35 hours–1. Bioplugging-induced formation damage negatively affecting the oil-recovery efficiency is also observed with an increase in the process run time. The screened microbe also exhibited the possibility of wettability alteration of sandstone-formation rock from mixed/oil-wet to water-wet. Thus, the present study provides an improved understanding of the combined effects of reservoir porosity, microbial kinetic, and key operational parameters on fundamental MEOR processes, which will better characterize and develop an effective strategy to determine the suitability of an MEOR technique in a typical sandstone reservoir. Moreover, the developed numerical model is easier to implement and produces faster results with relatively lower computational cost, which helps in making a quick decision before applying MEOR processes in the field.

Evaluation of Mechanistic Models for Nitrate Removal in Woodchip Bioreactors.

Woodchip bioreactors (WBRs) are increasingly being applied to remove nitrate from runoff. In this study, replicate columns with aged woodchips were subjected to a range of measured flow rates and influent nitrate concentrations with an artificial stormwater matrix. Dissolved oxygen (DO), nitrate, and dissolved organic carbon (DOC) were measured along the length of the columns. A multispecies reactive transport model with Michaelis-Menten kinetics was developed to explain the concentration profiles of DO, nitrate, and DOC. Four additional models were developed based on simplifying assumptions, and all five models were tested for their ability to predict nitrate concentrations in the experimental columns. Global sensitivity analysis and constrained optimization determined the set of parameters that minimized the root-mean-squared error (RMSE) between the model and the experimental data. A k-fold validation test revealed no statistical difference in RMSE for predicting nitrate concentrations between a zero-order model and the other multispecies reactive transport models tested. Additionally, the multispecies reactive transport models demonstrated no significant differences in predicting DO and DOC concentrations. These results suggest that denitrification in an aged woodchip bioreactor at constant temperature can effectively be modeled using zero-order kinetics when nitrate concentrations are >2 mg-N L-1. A multispecies model may be used if predicting DOC or DO concentrations is desired.

On the efficiency of the hybrid and the exact second-order sampling formulations of the EnKF: a reality-inspired 3-D test case for estimating biodegradation rates of chlorinated hydrocarbons at the port of Rotterdam

Abstract. This study considers the assimilation problem of subsurface contaminants at the port of Rotterdam in the Netherlands. It involves the estimation of solute concentrations and biodegradation rates of four different chlorinated solvents. We focus on assessing the efficiency of an adaptive hybrid ensemble Kalman filter and optimal interpolation (EnKF-OI) and the exact second-order sampling formulation (EnKFESOS) for mitigating the undersampling of the estimation and observation errors covariances, respectively. A multi-dimensional and multi-species reactive transport model is coupled to simulate the migration of contaminants within a Pleistocene aquifer layer located around 25 m below mean sea level. The biodegradation chain of chlorinated hydrocarbons starting from tetrachloroethene and ending with vinyl chloride is modeled under anaerobic environmental conditions for 5 decades. Yearly pseudo-concentration data are used to condition the forecast concentration and degradation rates in the presence of model and observational errors. Assimilation results demonstrate the robustness of the hybrid EnKF-OI, for accurately calibrating the uncertain biodegradation rates. When implemented serially, the adaptive hybrid EnKF-OI scheme efficiently adjusts the weights of the involved covariances for each individual measurement. The EnKFESOS is shown to maintain the parameter ensemble spread much better leading to more robust estimates of the states and parameters. On average, a well tuned hybrid EnKF-OI and the EnKFESOS respectively suggest around 48 and 21 % improved concentration estimates, as well as around 70 and 23 % improved anaerobic degradation rates, over the standard EnKF. Incorporating large uncertainties in the flow model degrades the accuracy of the estimates of all schemes. Given that the performance of the hybrid EnKF-OI depends on the quality of the background statistics, satisfactory results were obtained only when the uncertainty imposed on the background information is relatively moderate.

Numerical modelling of biophysicochemical effects on multispecies reactive transport in porous media involving Pseudomonas putida for potential microbial enhanced oil recovery application

pH and resident time of injected slug plays a critical role in characterizing the reservoir for potential microbial enhanced oil recovery (MEOR) application. To investigate MEOR processes, a multispecies (microbes–nutrients) reactive transport model in porous media was developed by coupling kinetic and transport model. The present work differs from earlier works by explicitly determining parametric values required for kinetic model by experimental investigations using Pseudomonas putida at different pH conditions and subsequently performing sensitivity analysis of pH, resident time and water saturation on concentrations of microbes, nutrients and biosurfactant within reservoir. The results suggest that nutrient utilization and biosurfactant production are found to be maximum at pH 8 and 7.5 respectively. It is also found that the sucrose and biosurfactant concentrations are highly sensitive to pH rather than reservoir microbial concentration, while at larger resident time and water saturation, the microbial and nutrient concentrations were lesser due to enhanced dispersion.

Seasonality of temperatures and redox zonations during bank filtration – A modeling approach

Bank filtration (BF) is a common technique for supplying drinking water, using the ability of the infiltration zone and aquifer passage to attenuate or degrade undesired substances that infiltrate from surface waters to groundwater abstraction wells. Temporal and spatial changes of temperatures and redox conditions are often the controlling factors for the fate and behavior of micropollutants during subsurface passage and consequently for the extracted raw water quality. A 2-dimensional cross-sectional heat transport and multi-species reactive transport model was set up to simulate the seasonally varying temperatures and redox conditions on the infiltration path at a bank filtration site in Berlin, Germany. The calibrated model was able to capture the observed variations in O2 and NO3− when considering temperature dependence of the redox reaction kinetics. The observed Mn2+- and Fe2+-concentrations were not well replicated by the model, presumably due to mineral reactions that were not accounted for in the simulations. SO42− was found to behave conservative, i.e., the observed concentration could be well simulated without any reactions. The simulations reveal the transience of BF systems with regard to temperatures and redox conditions, which has important implications for the BF quality and should therefore be accounted for.

Use of a multi-species reactive transport model to simulate chloride ingress in mortar exposed to NaCl solution or sea-water

Simulations of ion ingress in Portland cement mortar using a multi-species reactive mass transport model are compared with experimental test results. The model is an extended version of the Poisson–Nernst–Planck equations, accounting for chemical equilibrium. Saturated mortar samples were exposed after 8days of hydration to a NaCl-solution or natural sea-water in a laboratory controlled environment for the experimental part. The samples were analyzed for the total chloride content after 21, 90 and 180days of exposure, at varying depths from the exposed surface. The applicability of the reactive mass transport model is shown by comparing the simulation and experimental results. The tortuosity factor used in the simulations is adjusted to obtain the best reproduction of the experimental results. The model predicts the total chloride content satisfactorily, despite assumptions in the simulation like fixed hydration degree over time. Improvements and suggestions for further development of the model are discussed, e.g. extended hydration description, improved overall chemical description and a more strict use of the tortuosity factor.

Modeling reactive transport of reclaimed water through large soil columns with different low-permeability layers

The efficacy of different proportions of silt-loam/bentonite mixtures overlying a vadose zone in controlling solute leaching to groundwater was quantified. Laboratory experiments were carried out using three large soil columns, each packed with 200-cm-thick riverbed soil covered by a 2-cm-thick bentonite/silt-loam mixture as the low-permeability layer (with bentonite mass accounting for 12, 16 and 19 % of the total mass of the mixture). Reclaimed water containing ammonium (NH4 +), nitrate (NO3 −), organic matter (OM), various types of phosphorus and other inorganic salts was applied as inflow. A one-dimensional mobile–immobile multi-species reactive transport model was used to predict the preferential flow and transport of typical pollutants through the soil columns. The simulated results show that the model is able to predict the solute transport in such conditions. Increasing the amount of bentonite in the low-permeability layer improves the removal of NH4 + and total phosphorous (TP) because of the longer contact time and increased adsorption capacity. The removal of NH4 + and OM is mainly attributed to adsorption and biodegradation. The increase of TP and NO3 − concentration mainly results from discharge and nitrification in riverbed soils, respectively. This study underscores the role of low-permeability layers as barriers in groundwater protection. Neglect of fingers or preferential flow may cause underestimation of pollution risk.

A flexible uncertainty quantification method for linearly coupled multi-physics systems

This paper presents a novel approach to building an integrated uncertainty quantification (UQ) methodology suitable for modern-day component-based approach for multi-physics simulation development. Our “hybrid” UQ methodology supports independent development of the most suitable UQ method, intrusive or non-intrusive, for each physics module by providing an algorithmic framework to couple these “stochastic” modules for propagating “global” uncertainties. We address algorithmic and computational issues associated with the construction of this hybrid framework. We demonstrate the utility of such a framework on a practical application involving a linearly coupled multi-species reactive transport model.

A multi-species reactive transport model to estimate biogeochemical rates based on single-well push–pull test data

Push–pull tests are a popular technique to investigate various aquifer properties and microbial reaction kinetics in situ. Most previous studies have interpreted push–pull test data using approximate analytical solutions to estimate (generally first-order) reaction rate coefficients. Though useful, these analytical solutions may not be able to describe important complexities in rate data. This paper reports the development of a multi-species, radial coordinate numerical model (PPTEST) that includes the effects of sorption, reaction lag time and arbitrary reaction order kinetics to estimate rates in the presence of mixing interfaces such as those created between injected “push” water and native aquifer water. The model has the ability to describe an arbitrary number of species and user-defined reaction rate expressions including Monod/Michelis–Menten kinetics. The FORTRAN code uses a finite-difference numerical model based on the advection-dispersion-reaction equation and was developed to describe the radial flow and transport during a push–pull test. The accuracy of the numerical solutions was assessed by comparing numerical results with analytical solutions and field data available in the literature. The model described the observed breakthrough data for tracers (chloride and iodide-131) and reactive components (sulfate and strontium-85) well and was found to be useful for testing hypotheses related to the complex set of processes operating near mixing interfaces.

Effect of Uncertain Hydraulic Conductivity on the Simulated Fate and Transport of BTEX Compounds at a Field Site

A Monte Carlo analysis was conducted to investigate the effect of uncertain hydraulic conductivity on the fate and transport of BTEX compounds (benzene, toluene, ethyl benzene, and xylene) at a field site on Hill Air Force Base, Utah. Microbially mediated BTEX degradation has occurred at the site through multiple terminal electron-accepting processes, including aerobic respiration, denitrification, Fe(III) reduction, sulfate reduction, and methanogenesis degradation. Multiple realizations of the hydraulic conductivity field were generated and substituted into a multispecies reactive transport model developed and calibrated for the Hill AFB site in a previous study. Simulation results show that the calculated total BTEX masses (released from a constant-concentration source) that remain in the aquifer at the end of the simulation period statistically follow a lognormal distribution. In the first analysis (base case), the calculated total BTEX mass varies from a minimum of 12% less and a maximum of 60% more than that of the previously calibrated model. This suggests that the uncertainty in hydraulic conductivity can lead to significant uncertainties in modeling the fate and transport of BTEX. Geometric analyses of calculated plume configurations show that a higher BTEX mass is associated with wider lateral spreading, while a lower mass is associated with longer longitudinal extension. More BTEX mass in the aquifer causes either a large depletion of dissolved oxygen (DO) and NO{sub 3}{sup -}, or a large depletion of DO and a large production of Fe{sup 2+}, with moderately depleted NO{sub 3}{sup -}. In an additional analysis, the effect of varying degrees of aquifer heterogeneity and associated uncertainty is examined by considering hydraulic conductivity with different variances and correlation lengths. An increase in variance leads to a higher average BTEX mass in the aquifer, while an increase in correlation length results in a lower average. This observation is explained by relevant partitioning of BTEX into the aquifer from the LNAPL source. Although these findings may only be applicable to the field conditions considered in this study, the methodology used and insights gained are of general interest and relevance to other fuel-hydrocarbon natural-attenuation sites.

Natural attenuation of chlorinated ethene compounds: model development and field-scale application at the Dover site

A multi-dimensional and multi-species reactive transport model was developed to aid in the analysis of natural attenuation design at chlorinated solvent sites. The model can simulate several simultaneously occurring attenuation processes including aerobic and anaerobic biological degradation processes. The developed model was applied to analyze field-scale transport and biodegradation processes occurring at the Area-6 site in Dover Air Force Base, Delaware. The model was calibrated to field data collected at this site. The calibrated model reproduced the general groundwater flow patterns, and also, it successfully recreated the observed distribution of tetrachloroethene (PCE), trichloroethene (TCE), dichloroethylene (DCE), vinyl chloride (VC) and chloride plumes. Field-scale decay rates of these contaminant plumes were also estimated. The decay rates are within the range of values that were previously estimated based on lab-scale microcosm and field-scale transect analyses. Model simulation results indicated that the anaerobic degradation rate of TCE, source loading rate, and groundwater transport rate are the important model parameters. Sensitivity analysis of the model indicated that the shape and extent of the predicted TCE plume is most sensitive to transmissivity values. The total mass of the predicted TCE plume is most sensitive to TCE anaerobic degradation rates. The numerical model developed in this study is a useful engineering tool for integrating field-scale natural attenuation data within a rational modeling framework. The model results can be used for quantifying the relative importance of various simultaneously occurring natural attenuation processes.

Simulation of aerobic and anaerobic biodegradation processes at a crude oil spill site

A two‐dimensional, multispecies reactive solute transport model with sequential aerobic and anaerobic degradation processes was developed and tested. The model was used to study the field‐scale solute transport and degradation processes at the Bemidji, Minnesota, crude oil spill site. The simulations included the biodegradation of volatile and nonvolatile fractions of dissolved organic carbon by aerobic processes, manganese and iron reduction, and methanogenesis. Model parameter estimates were constrained by published Monod kinetic parameters, theoretical yield estimates, and field biomass measurements. Despite the considerable uncertainty in the model parameter estimates, results of simulations reproduced the general features of the observed groundwater plume and the measured bacterial concentrations. In the simulation, 46% of the total dissolved organic carbon (TDOC) introduced into the aquifer was degraded. Aerobic degradation accounted for 40% of the TDOC degraded. Anaerobic processes accounted for the remaining 60% of degradation of TDOC: 5% by Mn reduction, 19% by Fe reduction, and 36% by methanogenesis. Thus anaerobic processes account for more than half of the removal of DOC at this site.