Mart Oostrom

Movement and remediation of trichloroethylene in a saturated heterogeneous porous Medium. 1. Spill behavior and initial dissolution

Abstract An intermediate-scale flow cell experiment was conducted to study the flow of liquid and the transport of dissolved trichloroethylene (TCE) in a saturated, heterogeneous porous medium system. The 1.67-m long by 1.0-m high by 0.05-m wide flow cell was packed with three layers and five lenses consisting of four different sands. All lenses and layers had horizontal interfaces, except the lowest interface, which was pointed down in the middle. Groundwater flow was imposed by manipulating the water levels in two head chambers. Over 500 ml of dyed TCE was allowed to infiltrate at a constant rate into the porous medium from a narrow source located on the surface. A dual-energy gamma radiation system was used to determine TCE saturations at 1059 locations. Fluid samples were collected from 20 sampling ports to determine dissolved TCE concentrations. The TCE migrated downwards in the form of several relatively narrow (3–8 mm) fingers. Visual observations and measured TCE saturations indicated that the spilled TCE accumulated on top of, but did not penetrate into, fine-grained sand lenses and layers but that some TCE infiltrated into medium-grained sand lenses. This behavior is a result of the different nonwetting-fluid entry and permeability values of the sands. Most of the TCE finally pooled on top of a fine-grained sand layer located in the bottom part of the flow cell. A multifluid code (STOMP: subsurface transport over multiple phases), accounting for TCE entrapment, was used to simulate the movement of liquid TCE. Using independently obtained hydraulic parameter values, the code was able to qualitatively predict the observed behavior at the interfaces of the lenses and sand layers. Simulation results suggest that most of the liquid TCE at the lowest interface was in free, continuous form, while most of the other TCE remaining in the flow cell was entrapped and discontinuous. A simple pool dissolution model was used to predict observed dissolved TCE concentrations. Results show that the measured concentrations could only be predicted with unrealistically high transverse dispersivity values. The observed TCE concentrations are a result of a combination of entrapped and pool dissolution.

Comparison of Relative Permeability-Saturation-Pressure Parametric Models for Infiltration and Redistribution of a Light Nonaqueous-phase Liquid in Sandy Porous Media

Abstract To test and evaluate the ability of commonly used constitutive relations for multifluid flow predictions, results of numerical flow and transport simulations are compared to experimental data. Three quantitative experiments were conducted in 1-m-long vertical columns. The columns were filled with either a uniform sand, a sand with a broad particle-size distribution, or with a layered system where a layer of a course-textured uniform sand was placed in an otherwise finer-textured uniform sand. After establishing variably water-saturated conditions, a pulse of a light nonaqueous-phase liquid (LNAPL) was injected uniformly at a constant rate. Water and LNAPL saturations were measured as a function of time and elevation with a dual-energy gamma-radiation system. The infiltration and redistribution of the LNAPL were simulated with nonhysteretic and hysteretic parametric relative permeability-saturation-pressure (k-S-P) models. The models were calibrated using two-phase air-water retention data and an established scaling theory. The nonhysteretic Brooks-Corey k-S-P model, which utilizes the Burdine relative permeability model, yielded predictions that closely matched the experimental data. Use of the nonhysteretic and hysteretic k-S-P models, based on the van Genuchten S-P relations and k-S relations derived from the Mualem relative permeability model, did not agree as well with the experimental data as those obtained with the Brooks-Corey k-S-P model. Explanations for the differences in performance of the three tested parametric k-S-P models are proposed.

Pore-scale study of transverse mixing induced CaCO3 precipitation and permeability reduction in a model subsurface sedimentary system

A microfluidic pore structure etched into a silicon wafer was used as a two-dimensional model subsurface sedimentary system (i.e., micromodel) to study mineral precipitation and permeability reduction relevant to groundwater remediation and geological carbon sequestration. Solutions containing CaCl(2) and Na(2)CO(3) at four different saturation states (Ω = [Ca(2+)][CO(3)(2-)]/K(spCaCO(3))) were introduced through two separate inlets, and they mixed by diffusion transverse to the main flow direction along the center of the micromodel resulting in CaCO(3) precipitation. Precipitation rates increased and the total amount of precipitates decreased with increasing saturation state, and only vaterite and calcite crystals were formed (no aragonite). The relative amount of vaterite increased from 80% at the lowest saturation state (Ω(v) = 2.8 for vaterite) to 95% at the highest saturation state (Ω(v) = 4.5). Fluorescent tracer tests conducted before and after CaCO(3) precipitation indicate that pore spaces were occluded by CaCO(3) precipitates along the transverse mixing zone, thus substantially reducing porosity and permeability, and potentially limiting transformation from vaterite to the more stable calcite. The results suggest that mineral precipitation along plume margins can decrease both reactant mixing during groundwater remediation, and injection and storage efficiency during CO(2) sequestration.

Mass-removal and mass-flux-reduction behavior for idealized source zones with hydraulically poorly-accessible immiscible liquid.

A series of flow-cell experiments was conducted to investigate aqueous dissolution and mass-removal behavior for systems wherein immiscible liquid was non-uniformly distributed in physically heterogeneous source zones. The study focused specifically on characterizing the relationship between mass flux reduction and mass removal for systems for which immiscible liquid is poorly accessible to flowing water. Two idealized scenarios were examined, one wherein immiscible liquid at residual saturation exists within a lower-permeability unit residing in a higher-permeability matrix, and one wherein immiscible liquid at higher saturation (a pool) exists within a higher-permeability unit adjacent to a lower-permeability unit. The results showed that significant reductions in mass flux occurred at relatively moderate mass-removal fractions for all systems. Conversely, minimal mass flux reduction occurred until a relatively large fraction of mass (>80%) was removed for the control experiment, which was designed to exhibit ideal mass removal. In general, mass flux reduction was observed to follow an approximately one-to-one relationship with mass removal. Two methods for estimating mass-flux-reduction/mass-removal behavior, one based on system-indicator parameters (ganglia-to-pool ratio) and the other a simple mass-removal function, were used to evaluate the measured data. The results of this study illustrate the impact of poorly accessible immiscible liquid on mass-removal and mass-flux processes, and the difficulties posed for estimating mass-flux-reduction/mass-removal behavior.

Movement and remediation of trichloroethylene in a saturated, heterogeneous porous medium: 2. Pump-and-treat and surfactant flushing

An intermediate-scale flow cell experiment was conducted to remove a liquid trichloroethylene (TCE) spill from a saturated, heterogeneous porous medium using pump-and-treat (P&T) as well as surfactant flushing (SF) techniques. Dissolved TCE concentrations were measured at 20 locations, while fluid saturations were obtained with a dual-energy gamma scanner. The behavior of the TCE spill has been described by Oostrom et al. (1998b) [Oostrom, M., Hofstee, C., Walker, R.C., Dane, J.H., 1998b. Movement and remediation of TCE in a saturated heterogeneous porous medium: 1. Spill behavior and initial dissolution, this issue.]. A total of six alternating P&T and SF periods were used to remediate the flow cell. A two-well system, consisting of an injection and an extraction well, was used during the first five remediation periods. For the last SF period, a three-well system was employed with two injection wells and one extraction well. During the first P&T period, most entrapped TCE was removed, but TCE saturations in a substantial pool on top of a fine-grained sand layer were largely unaffected. During the first SF period, a dense plume was formed containing solubilized TCE which partially sank into the fine-grained sand. In addition, unstable fingers developed below the liquid TCE in the pool. In several samples, small TCE droplets were found, indicating mobilization of TCE. Most of the samples with concentrations larger than 5000 ppm had a milky, emulsion-like appearance. The SF considerably reduced the amount of TCE in the pool on top of the fine-grained sand. During the second P&T period, plume sinking and instabilities were not observed. After starting the second SF period, some unstable fingering and plume sinking resumed, starting at the upstream end of the TCE in the pool. The saturation distribution obtained after the second SF period was quite similar to the one obtained after the first SF period, indicating that additional removal of TCE through SF was difficult as a result of the limited accessibility of the TCE in the pool. A gamma scan, obtained after three weeks of pumping using the three-well configuration, shows that all the liquid TCE had been removed from the coarse-grained sand. Computations based on extraction rates and measured TCE concentrations show that only about 60% of the injected TCE was removed from the cell during the experiment. Part of the missing 40% might have moved downwards into the fine-grained sand as a result of pure phase mobilization. The experimental results suggest that besides the positive effects of solubilization, possible detrimental processes such as pure phase mobilization and dense aqueous-phase plume behavior should be considered during SF.

Infiltration and redistribution of perchloroethylene in partially saturated, stratified porous media

Abstract Contamination of the subsurface by nonaqueous phase liquids (NAPLs) is a widespread problem. To investigate the behavior of a nonspreading, dense NAPL (DNAPL) in the vadose zone, we conducted perchloroethylene (PCE) infiltration experiments in nominally 1- and 2-dimensional (D), stratified porous media. In addition, the usefulness and limitations of a multifluid flow simulator to describe PCE infiltration and redistribution under the experimental conditions were tested. The physical simulations were conducted in a column (1-D) and a flow container (2-D) which were packed with two distinct layers of coarse-grained sand and a fine-grained sand layer in between. Volumetric water and PCE contents were determined with a fully automated dual-energy gamma radiation system. While migrating through the drier parts of the coarse-grained sand layers, PCE appeared to wet the water–air interface rather than displacing any water. In the wetter parts of the porous medium, PCE displaced water and behaved as a true nonwetting fluid. PCE showed a limited response to gradients in capillary pressure and rather high values for the volumetric PCE content were measured in the fine-grained sand layers. This was attributed to the nonspreading nature of PCE. The multifluid flow simulator appeared to predict the initial PCE movement in the vadose zone reasonably well. However, the model was not capable of predicting the final amounts of PCE retained in either the unsaturated or saturated part of the flow domain, mainly because the simulator does not consider the nonspreading flow behavior of NAPLs.

Flow Behavior and Residual Saturation Formation of Liquid Carbon Tetrachloride in Unsaturated Heterogeneous Porous Media

The formation of residual, discontinuous nonaqueous phase liquids (NAPLs) in the vadose zone is a process that is not well understood. To obtain data that can be used to study the development of a residual NAPL saturation in the vadose zone and to test current corresponding models, detailed transient experiments were conducted in intermediate-scale columns and flow cell. The column experiments were conducted to determine residual carbon tetrachloride (CCl(4)) saturations of two sands and to evaluate the effect of CCl(4) vapors on the water distribution. In the intermediate-scale flow cell experiment, a rectangular zone of the fine-grained sand was packed in an otherwise medium-grained matrix. A limited amount of CCl(4) was injected from a small source and allowed to redistribute until a pseudo steady state situation had developed. A dual-energy gamma radiation system was used to determine fluid saturations at numerous locations. The experiments clearly demonstrated the formation of residual CCl(4) saturations in both sands. Simulations with an established multifluid flow simulator show the shortcomings of current relative permeability-saturation-capillary pressure (k-S-P) models. The results indicate that nonspreading behavior of NAPLs should be implemented in simulators to account for the formation of residual saturations.

Theoretical estimation of free and entrapped nonwetting–wetting fluid interfacial areas in porous media

Abstract Fluid–fluid interfacial areas play important roles in numerous subsurface processes such as dissolution, volatilization, and adsorption. Integral expressions have been derived to estimate both entrapped (discontinuous) and free (continuous) nonwetting fluid–wetting fluid specific interfacial areas in porous media. The expressions, compatible with widely used capillary head-saturation and entrapment models, require information on capillary head-saturation relation parameters, porosity, and fluid-pair interfacial tension. In addition, information on the maximum entrapped nonwetting fluid saturation as well as the main drainage branch reversal point for water and total liquid saturations is necessary to estimate entrapped fluid interfacial areas. Implementation of the interfacial area equations in continuum-based multifluid flow simulators is straightforward since no additional parameters are needed than those required by the simulators to complete the multifluid flow computations. A limited sensitivity analysis, based on experimentally obtained parameter values, showed that imposed variations resulted in logical and consistent changes in predicted specific interfacial areas for both entrapped and free nonwetting fluid–wetting fluid systems. A direct comparison with published experimental work to test the derived expressions was limited to free air–water systems and yielded reasonable results. Such comparisons are often not possible because of the lack of information given on retention parameters, and variables used to determine nonwetting fluid entrapment. This contribution is dedicated to John W. Cary.

Assessing performance and closure for soil vapor extraction: Integrating vapor discharge and impact to groundwater quality

Soil vapor extraction (SVE) is typically effective for removal of volatile contaminants from higher-permeability portions of the vadose zone. However, contamination in lower-permeability zones can persist due to mass transfer processes that limit the removal effectiveness. After SVE has been operated for a period of time and the remaining contamination is primarily located in lower-permeability zones, the remedy performance needs to be evaluated to determine whether the SVE system should be optimized, terminated, or transitioned to another technology to replace or augment SVE. Numerical modeling of vapor-phase contaminant transport was used to investigate the correlation between measured vapor-phase mass discharge, MF(r), from a persistent, vadose-zone contaminant source and the resulting groundwater contaminant concentrations. This relationship was shown to be linear, and was used to directly assess SVE remediation progress over time and to determine the level of remediation in the vadose zone necessary to protect groundwater. Although site properties and source characteristics must be specified to establish a unique relation between MF(r) and the groundwater contaminant concentration, this correlation provides insight into SVE performance and support for decisions to optimize or terminate the SVE operation or to transition to another type of treatment.

Pore-Scale and Multiscale Numerical Simulation of Flow and Transport in a Laboratory-Scale Column

Pore-scale models are useful for studying relationships between fundamental processes and phenomena at larger (i.e., Darcy) scales. However, the size of domains that can be simulated with explicit pore-scale resolution is limited by computational and observational constraints. Direct numerical simulation of pore-scale flow and transport is typically performed on millimeter-scale volumes at which X-ray computed tomography (XCT), often used to characterize pore geometry, can achieve micrometer resolution. In contrast, laboratory experiments that measure continuum properties are typically performed on decimeter-scale columns. At this scale, XCT resolution is coarse (tens to hundreds of micrometers) and prohibits characterization of small pores and grains. We performed simulations of pore-scale processes over a decimeter-scale volume of natural porous media with a wide range of grain sizes, and compared to results of column experiments using the same sample. Simulations were conducted using high-performance codes executed on a supercomputer. Two approaches to XCT image segmentation were evaluated, a binary (pores and solids) segmentation and a ternary segmentation that resolved a third category (porous solids with pores smaller than the imaged resolution). We used a multiscale Stokes-Darcy simulation method to simulate the combination of Stokes flow in large open pores and Darcy-like flow in porous solid regions. Flow and transport simulations based on the binary segmentation were inconsistent with experimental observations because of overestimation of large connected pores. Simulations based on the ternary segmentation provided results that were consistent with experimental observations, demonstrating our ability to successfully model pore-scale flow over a column-scale domain.