Amir Raoof

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.

Effect of mean network coordination number on dispersivity characteristics

In this study, we investigate the role of topology on the macroscopic (centimeter scale) dispersion characteristics derived from pore-network models. We consider 3D random porous networks extracted from a regular cubic lattice with coordination number distributed in accordance with real porous structures. We use physically consistent rules including ideal mixing in pore bodies, molecular diffusion, and Taylor dispersion in pore throats to simulate transport at the pore-scale level. Fundamental properties of porous networks are based on statistical distributions of basic parameters. Theoretical calculations demonstrate strong correspondence with data obtained from numerical experiments. For low coordination numbers, we observe normal transport in porous networks. Anomalous effects expressed by tailing in concentration evolution are seen for higher coordination numbers. We find that the mean network coordination number has significant influence on averaged characteristics of porous networks such as geometric and hydraulic dispersivity, while other topological properties are of less significance. We give an explicit formula that describes the decrease of geometric dispersivity with growing mean coordination number. The results demonstrate the importance of network topology for models for flow and transport in porous media.

Oxidation of volatile organic vapours in air by solid potassium permanganate

Volatile organic compounds (VOCs) may frequently contaminate groundwater and pose threat to human health when migrating into the unsaturated soil zone and upward to the indoor air. The kinetic of chemical oxidation has been investigated widely for dissolved VOCs in the saturated zone. But, so far there have been few studies on the use of in situ chemical oxidation (ISCO) of vapour phase contaminants. In this study, batch experiments were carried out to evaluate the oxidation of trichloroethylene (TCE), ethanol, and toluene vapours by solid potassium permanganate. Results revealed that solid potassium permanganate is able to transform the vapour of these compounds into harmless oxidation products. The degradation rates for TCE and ethanol were higher than for toluene. The degradation process was modelled using a kinetic model, linear in the gas concentration of VOC [ML(-3)] and relative surface area of potassium permanganate grains (surface area of potassium permanganate divided by gas volume) [L(-1)]. The second-order reaction rate constants for TCE, ethanol, and toluene were found to be equal to 2.0×10(-6) cm s(-1), 1.7×10(-7) cm s(-1), and 7.0×10(-8) cm s(-1), respectively.

Oxidation of trichloroethylene, toluene, and ethanol vapors by a partially saturated permeable reactive barrier

The mitigation of volatile organic compound (VOC) vapors in the unsaturated zone largely relies on the active removal of vapor by ventilation. In this study we considered an alternative method involving the use of solid potassium permanganate to create a horizontal permeable reactive barrier for oxidizing VOC vapors. Column experiments were carried out to investigate the oxidation of trichloroethylene (TCE), toluene, and ethanol vapors using a partially saturated mixture of potassium permanganate and sand grains. Results showed a significant removal of VOC vapors due to the oxidation. We found that water saturation has a major effect on the removal capacity of the permeable reactive layer. We observed a high removal efficiency and reactivity of potassium permanganate for all target compounds at the highest water saturation (Sw=0.6). A change in pH within the reactive layer reduced oxidation rate of VOCs. The use of carbonate minerals increased the reactivity of potassium permanganate during the oxidation of TCE vapor by buffering the pH. Reactive transport of VOC vapors diffusing through the permeable reactive layer was modeled, including the pH effect on the oxidation rates. The model accurately described the observed breakthrough curve of TCE and toluene vapors in the headspace of the column. However, miscibility of ethanol in water in combination with produced water during oxidation made the modeling results less accurate for ethanol. A linear relationship was found between total oxidized mass of VOC vapors per unit volume of permeable reactive layer and initial water saturation. This behavior indicates that pH changes control the overall reactivity and longevity of the permeable reactive layer during oxidation of VOCs. The results suggest that field application of a horizontal permeable reactive barrier can be a viable technology against upward migration of VOC vapors through the unsaturated zone.

Virus-sized colloid transport in a single pore: Model development and sensitivity analysis

A mathematical model is developed to simulate the transport and deposition of virus-sized colloids in a cylindrical pore throat considering various processes such as advection, diffusion, colloid-collector surface interactions and hydrodynamic wall effects. The pore space is divided into three different regions, namely, bulk, diffusion and potential regions, based on the dominant processes acting in each of these regions. In the bulk region, colloid transport is governed by advection and diffusion whereas in the diffusion region, colloid mobility due to diffusion is retarded by hydrodynamic wall effects. Colloid-collector interaction forces dominate the transport in the potential region where colloid deposition occurs. The governing equations are non-dimensionalized and solved numerically. A sensitivity analysis indicates that the virus-sized colloid transport and deposition is significantly affected by various pore-scale parameters such as the surface potentials on colloid and collector, ionic strength of the solution, flow velocity, pore size and colloid size. The adsorbed concentration and hence, the favorability of the surface for adsorption increases with: (i) decreasing magnitude and ratio of surface potentials on colloid and collector, (ii) increasing ionic strength and (iii) increasing pore radius. The adsorbed concentration increases with increasing Pe, reaching a maximum value at Pe=0.1 and then decreases thereafter. Also, the colloid size significantly affects particle deposition with the adsorbed concentration increasing with increasing particle radius, reaching a maximum value at a particle radius of 100nm and then decreasing with increasing radius. System hydrodynamics is found to have a greater effect on larger particles than on smaller ones. The secondary minimum contribution to particle deposition has been found to increase as the favorability of the surface for adsorption decreases. The sensitivity of the model to a given parameter will be high if the conditions are favorable for adsorption. The results agree qualitatively with the column-scale experimental observations available in the literature. The current model forms the building block in upscaling colloid transport from pore scale to Darcy scale using Pore-Network Modeling.

Correlation equations for average deposition rate coefficients of nanoparticles in a cylindrical pore

Nanoparticle deposition behavior observed at the Darcy scale represents an average of the processes occurring at the pore scale. Hence, the effect of various pore-scale parameters on nanoparticle deposition can be understood by studying nanoparticle transport at pore scale and upscaling the results to the Darcy scale. In this work, correlation equations for the deposition rate coefficients of nanoparticles in a cylindrical pore are developed as a function of nine pore-scale parameters: the pore radius, nanoparticle radius, mean flow velocity, solution ionic strength, viscosity, temperature, solution dielectric constant, and nanoparticle and collector surface potentials. Based on dominant processes, the pore space is divided into three different regions, namely, bulk, diffusion, and potential regions. Advection-diffusion equations for nanoparticle transport are prescribed for the bulk and diffusion regions, while the interaction between the diffusion and potential regions is included as a boundary condition. This interaction is modeled as a first-order reversible kinetic adsorption. The expressions for the mass transfer rate coefficients between the diffusion and the potential regions are derived in terms of the interaction energy profile. Among other effects, we account for nanoparticle-collector interaction forces on nanoparticle deposition. The resulting equations are solved numerically for a range of values of pore-scale parameters. The nanoparticle concentration profile obtained for the cylindrical pore is averaged over a moving averaging volume within the pore in order to get the 1-D concentration field. The latter is fitted to the 1-D advection-dispersion equation with an equilibrium or kinetic adsorption model to determine the values of the average deposition rate coefficients. In this study, pore-scale simulations are performed for three values of Peclet number, Pe = 0.05, 5, and 50. We find that under unfavorable conditions, the nanoparticle deposition at pore scale is best described by an equilibrium model at low Peclet numbers (Pe = 0.05) and by a kinetic model at high Peclet numbers (Pe = 50). But, at an intermediate Pe (e.g., near Pe = 5), both equilibrium and kinetic models fit the 1-D concentration field. Correlation equations for the pore-averaged nanoparticle deposition rate coefficients under unfavorable conditions are derived by performing a multiple-linear regression analysis between the estimated deposition rate coefficients for a single pore and various pore-scale parameters. The correlation equations, which follow a power law relation with nine pore-scale parameters, are found to be consistent with the column-scale and pore-scale experimental results, and qualitatively agree with the colloid filtration theory. These equations can be incorporated into pore network models to study the effect of pore-scale parameters on nanoparticle deposition at larger length scales such as Darcy scale.

The Use of Numerical Flow and Transport Models in Environmental Analyses

This chapter provides an overview of alternative approaches for modeling water flow and contaminant transport problems in soils and groundwater. Special focus is on flow and transport processes in the variably saturated vadose zone between the soil surface and the groundwater table. The governing flow and transport equations are discussed for both equilibrium and nonequilibrium flow conditions, followed by three examples. The first example shows how one-dimensional root-zone modeling can be used to estimate short- and long-term recharge rates, including contaminant transport through the vadose zone. A second example illustrates a two-dimensional application involving drip irrigation, while the third example deals with two-dimensional nonequilibrium transport of a pesticide in a tile-drained field soil. Also discussed are alternative pore-scale modeling approaches that may provide a better understanding of the basic physical and geochemical processes affecting fluid flow and contaminant transport in saturated and variably saturated media.

Pore-scale study of flow rate on colloid attachment and remobilization in a saturated micromodel

Colloid attachment is an important retention mechanism. It is influenced by colloid size, pore size, and flow rate, among other factors. In this work, we studied colloid attachment experimentally under various flow rates, as well as colloid release in response to a rapid change of flow rate. Colloid transport experiments under saturated conditions and with different flow rates were conducted in a physical micromodel. The micromodel was made of polydimethylsiloxane (PDMS), which is a hydrophobic polymer. Colloids were hydrophilic fluorescent carboxylate-modified polystyrene latex microspheres with a mean diameter of 300 nm. We could directly observe the movement of colloids within the pores using a confocal microscope. We also obtained concentration breakthrough curves by measuring the fluorescence intensity at the outlet of the micromodel. In addition, our experiments were simulated using a pore-network modeling, PoreFlow, based on the pore structure of the micromodel. Local colloid concentrations were calculated by solving local mass balance equations for all network elements and then averaging resulting concentrations over the whole micromodel. The measured breakthrough curves were successfully simulated using PoreFlow. Observed and calculated breakthrough curves showed that colloid attachment rate was smaller for larger flow rate. Temporally enhance colloid release (remobilization of attached colloids) was observed when the flow rate was increased by a factor of 10. But no colloid remobilization was observed when the flow rate decreased by a factor of 10.

Evaluation of a horizontal permeable reactive barrier for preventing upward diffusion of volatile organic compounds through the unsaturated zone.

Permeable reactive barriers are commonly used to treat contaminant plumes in the saturated zone. However, no known applications of horizontal permeable reactive barriers (HPRBs) exist for oxidizing volatile organic compounds (VOCs) in the unsaturated zone. In this study, laboratory column experiments were carried out to investigate the ability of a HPRB containing solid potassium permanganate, to oxidize the vapors of trichloroethylene (TCE), toluene, and ethanol migrating upward from a contaminated saturated zone. Results revealed that an increase in initial water saturation and HPRB thickness strongly affected the removal efficiency of the HPRB. Installing the HPRB relatively close to the water table was more effective due to the high background water content and enhanced diffusion of protons and/or hydroxides away from the HPRB. Inserting the HPRB far above the water table caused rapid changes in pH within the HPRB, leading to lower oxidation rates. The pH effects were included in a reactive transport model, which successfully simulated the TCE and toluene experimental observations. Simulations for ethanol were not affected by pH due to condensation of water during ethanol oxidation, which caused some dilution in the HRPB.

Water Curtain System Pre-design for Crude Oil Storage URCs: A Numerical Modeling and Genetic Programming Approach

In this paper the main criteria of the water curtain system for unlined rock caverns (URCs) is described. By the application of numerical modeling and genetic programming (GP), a method for water curtain system pre-design for Iranian crude oil storage URCs (common dimension worldwide) is presented. A comprehensive set of numerical simulations is performed using the finite element based commercial software (COMSOL 5.1) where the results are used as database for genetic programming. Describing equations of water inflow to the filled and empty caverns and water production rate of water curtain boreholes are generated using GP. By equating the proposed equations to each other, water curtain system can be pre-designed. Relative error of the generated GP equations shows their ability and accuracy. Applying a standard regression coefficient method, sensitivity analysis of parameters related to water curtain performance and water inflow to the caverns is performed as well. The results help the design of the water curtain system for crude oil storage caverns worldwide.