Kevin G. Mumford

Mass flux from a non-aqueous phase liquid pool considering spontaneous expansion of a discontinuous gas phase

The partitioning of non-aqueous phase liquid (NAPL) compounds to a discontinuous gas phase results in the repeated spontaneous expansion, snap-off, and vertical mobilization of the gas phase. This mechanism has the potential to significantly affect the mass transfer processes that control the dissolution of NAPL pools by increasing the vertical transport of NAPL mass and increasing the total mass transfer rate from the surface of the pool. The extent to which this mechanism affects mass transfer from a NAPL pool depends on the rate of expansion and the mass of NAPL compound in the gas phase. This study used well-controlled bench-scale experiments under no-flow conditions to quantify for the first time the expansion of a discontinuous gas phase in the presence of NAPL. Air bubbles placed in glass vials containing NAPL increased significantly in volume, from a radius of 1.0 mm to 2.0 mm over 215 days in the presence of tetrachloroethene (PCE), and from a radius of 1.2 mm to 2.3 mm over 22 days in the presence of trans-1,2-dichloroethene (tDCE). A one-dimensional mass transfer model, fit to the experimental data, showed that this expansion could result in a mass flux from the NAPL pool that was similar in magnitude to the mass flux expected for the dissolution of a NAPL pool in a two-fluid (NAPL and water) system. Conditions favouring the significant effect of a discontinuous gas phase on mass transfer were identified as groundwater velocities less than approximately 0.01 m/day, and a gas phase that covers greater than approximately 10% of the pool surface area and is located within approximately 0.01 m of the pool surface. Under these conditions the mass transfer via a discontinuous gas phase is expected to affect, for example, efforts to locate NAPL source zones using aqueous concentration data, and predict the lifetime and risk associated with NAPL source zones in a way that is not currently included in the common conceptual models used to assess NAPL-contaminated sites.

Gas production and transport during bench-scale electrical resistance heating of water and trichloroethene.

The effective remediation of chlorinated solvent source zones using in situ thermal treatment requires successful capture of gas that is produced. Replicate electrical resistance heating experiments were performed in a thin bench-scale apparatus, where water was boiled and pooled dense non-aqueous phase liquid (DNAPL) trichloroethene (TCE) and water were co-boiled in unconsolidated silica sand. Quantitative light transmission visualization was used to assess gas production and transport mechanisms. In the water boiling experiments, nucleation, growth and coalescence of the gas phase into connected channels were observed at critical gas saturations of Sgc=0.233±0.017, which allowed for continuous gas transport out of the sand. In experiments containing a colder region above a target heated zone, condensation prevented the formation of steam channels and discrete gas clusters that mobilized into colder regions were trapped soon after discontinuous transport began. In the TCE-water experiments, co-boiling at immiscible fluid interfaces resulted in discontinuous gas transport above the DNAPL pool. Redistribution of DNAPL was also observed above the pool and at the edge of the vapor front that propagated upwards through colder regions. These results suggest that the subsurface should be heated to water boiling temperatures to facilitate gas transport from specific locations of DNAPL to extraction points and reduce the potential for DNAPL redistribution. Decreases in electric current were observed at the onset of gas phase production, which suggests that coupled electrical current and temperature measurements may provide a reliable metric to assess gas phase development.

IN SITU THERMAL TREATMENT OF CHLORINATED SOLVENT SOURCE ZONES

Combining in situ heating with physical recovery, chemical reaction and biodegradation processes has led to a spectrum of in situ thermal remediation options for the cleanup of soils, rock and groundwater impacted by dense nonaqueous phase liquids. The growth in the application and understanding of these technologies over the past two decades has been significant – to the point that their potential application is considered for many sites having short target cleanup time frames (less than a few years) and for contaminants that are not accessible by other cleanup technologies (such as mass diffused into fine-grained media). This chapter presents an overview of the most practiced thermal remediation technologies. The chapter then provides a synthesis of the available data from several field applications, summarizes the lessons learned to date and finally summarizes the current understanding of their performance presents several case studies. of well-monitored field-scale applications.

Laboratory study of non-aqueous phase liquid and water co-boiling during thermal treatment.

In situ thermal treatment technologies, such as electrical resistance heating and thermal conductive heating, use subsurface temperature measurements in addition to the analysis of soil and groundwater samples to monitor remediation performance. One potential indication of non-aqueous phase liquid (NAPL) removal is an increase in temperature following observations of a co-boiling plateau, during which subsurface temperatures remain constant as NAPL and water co-boil. However, observed co-boiling temperatures can be affected by the composition of the NAPL and the proximity of the NAPL to the temperature measurement location. Results of laboratory heating experiments using single-component and multi-component NAPLs showed that local-scale temperature measurements can be mistakenly interpreted as an indication of the end of NAPL-water co-boiling, and that significant NAPL saturations (1% to 9%) remain despite observed increases in temperature. Furthermore, co-boiling of multi-component NAPL results in gradually increasing temperature, rather than a co-boiling plateau. Measurements of gas production can serve as a complementary metric for assessing NAPL removal by providing a larger-scale measurement integrated over multiple smaller-scale NAPL locations. Measurements of the composition of the NAPL condensate can provide ISTT operators with information regarding the progress of NAPL removal for multi-component sources.

Characterization of Transparent Soil for Use in Heat Transport Experiments

Heat transport in the geosphere is important in applications of geothermal energy systems, thermal remediation technologies, and design of energy foundations. The study of these applications would benefit significantly from the ability to collect temperature data from within the porous media system, and at high spatial and temporal resolutions. Temperature measurements made using conventional probes have high temporal resolution but are limited in their spatial resolution. Higher-resolution methods, such as thermal imaging, are limited to measurements of an exposed face of an experiment. This paper presents the development of a technique for measuring temperature using transparent soil. In typical transparent soil, the refractive indices of the soil particles and the pore fluid are matched, creating invisible soil particles when saturated. However, because the refractive indices of the soil particles and pore fluid are different functions of temperature, the degree of transparency decreases as the temperature increases or decreases from the transparency temperature. As such, changes in transparency are detected by digital photographs and can be calibrated and used to measure temperature. This paper presents relationships between temperature and normalized pixel intensity for two oil-fused silica combinations. One combination used an oil mixture with a transparency temperature of 25°C and the other, which was constructed using one of the oils in the mixture, has a transparency temperature of 4°C. The results show that there must be at least a 10°C differential from the transparency temperature to ensure a linear relationship between temperature and normalized pixel intensity. The capabilities of transparent soil constructed with the second oil are displayed in two laboratory experiments, which provide direct comparisons between transparent soil, conventional temperature probes, and thermal imaging. The results show the transparent soil provides reliable temperature fields across the experimental domain at high spatial and temporal resolutions.

Factors affecting gas migration and contaminant redistribution in heterogeneous porous media subject to electrical resistance heating.

A series of intermediate-scale laboratory experiments were completed in a two-dimensional flow cell to investigate gas production and migration during the application of electrical resistance heating (ERH) for the removal of dense non-aqueous phase liquids (DNAPLs). Experiments consisted of heating water in homogeneous silica sand and heating 270 mL of trichloroethene (TCE) and chloroform (CF) DNAPL pools in heterogeneous silica sands, both under flowing groundwater conditions. Spatial and temporal distributions of temperature were measured using thermocouples and observations of gas production and migration were collected using front-face image capture throughout the experiments. Post-treatment soil samples were collected and analyzed to assess DNAPL removal. Results of experiments performed in homogeneous sand subject to different groundwater flow rates showed that high groundwater velocities can limit subsurface heating rates. In the DNAPL pool experiments, temperatures increased to achieve DNAPL-water co-boiling, creating estimated gas volumes of 131 and 114 L that originated from the TCE and CF pools, respectively. Produced gas migrated vertically, entered a coarse sand lens and subsequently migrated laterally beneath an overlying capillary barrier to outside the heated treatment zone where 31-56% of the original DNAPL condensed back into a DNAPL phase. These findings demonstrate that layered heterogeneity can potentially facilitate the transport of contaminants outside the treatment zone by mobilization and condensation of gas phases during ERH applications. This underscores the need for vapor phase recovery and/or control mechanisms below the water table during application of ERH in heterogeneous porous media during the co-boiling stage, which occurs prior to reaching the boiling point of water.

A three-dimensional numerical model for linking community-wide vapour risks

A three-dimensional (3D) numerical model that couples contaminant transport in the saturated zone to vapour transport in the vadose zone and vapour intrusion into buildings was developed. Coupling these processes allows the simulation of vapour intrusion, arising from volatilization at the water table, associated with temporally and spatially variable groundwater plumes. In particular, the model was designed to permit, for the first time, 3D simulations of risk at receptors located in the wider community (i.e., kilometre scale) surrounding a contaminated site. The model can account for heterogeneous distributions of permeability, fraction organic carbon, sorption and biodegradation in the vadose and saturated zones. The model formulation, based upon integration of a number of widely accepted models, is presented along with verification and benchmarking tests. In addition, a number of exploratory simulations of benzene and naphthalene transport in a 1000 m long domain (aquifer cross-section: 500 m×14 m) are presented, which employed conservative assumptions consistent with the development of regulatory guidance. Under these conservative conditions, these simulations demonstrated, for example, that whether houses in the community were predicted to be impacted by groundwater and indoor air concentrations exceeding regulatory standards strongly depended on their distance downgradient from the source and lateral distance from the plume centreline. In addition, this study reveals that the degree of reduction in source concentration (i.e., remediation) required to achieve compliance with standards is less if the risk receptor is in the wider community than at the site boundary. However, these example scenarios suggest that, even considering community receptors, sources with initially high concentrations still required substantial remediation (i.e., >99% reductions in source concentration). Overall, this work provides insights and a new tool for considering the relationships between contaminated site source zones and community-wide risk assessment that allows for development of policies and technical approaches for contaminated site management. It is anticipated that this coupled model not only will allow significant convenience, for example in running suites of Monte Carlo simulations for complex scenarios, but will also allow the investigation of vapour intrusion under conditions where soil gas concentrations may change over the same timescale as an evolving plume.

Bubble-Facilitated VOC Transport from LNAPL Smear Zones and Its Potential Effect on Vapor Intrusion

Most conceptual and mathematical models of soil vapor intrusion assume that the transport of volatile organic compounds (VOCs) from a source toward a building is limited by diffusion through the soil gas. Under conditions where advection occurs, transport rates are higher and can lead to higher indoor air concentrations. Advection-dominated conditions can be created by gas bubble flow in the saturated zone. A series of laboratory column experiments were conducted to measure mass flux due to bubble-facilitated VOC transport from light nonaqueous phase liquid (LNAPL) smear zones. Smear zones that contained both LNAPL residual and trapped gas, as well as those that contained only LNAPL residual, were investigated. Results showed that the VOC mass flux due to bubble-facilitated transport was orders-of-magnitude higher than under diffusion-limited conditions. Results also showed that the mass flux due to bubble-facilitated transport was intermittent, and increased with an increased supply of dissolved gases.

Laboratory study of creosote removal from sand at elevated temperatures

In situ thermal treatment (ISTT) technologies have been applied at sites impacted by non-aqueous phase liquids (NAPLs). There is a need to establish expectations for the treatment of semi-volatile NAPLs, including those consisting primarily of polycyclic aromatic hydrocarbons (PAHs), and the potential benefits and limitations of partial NAPL removal. A series of laboratory experiments was conducted to investigate NAPL removal and soil concentrations during the heating of creosote-impacted sand, as well as aqueous concentrations during post-heating dissolution. The results showed co-boiling near the water boiling temperature due to the low volatility of most creosote components, with limited decreases in NAPL saturation (from 30% to 21% of the pore space). Decreases in soil concentration were more substantial than decreases in NAPL saturation (by a factor of 2-180), with greater removal for higher-volatility components at higher treatment temperatures. Results of the dissolution experiments showed mixed results, with decreases in the aqueous concentrations for 12 of 15 components, but increases in aqueous concentrations for phenanthrene, fluoranthene and pyrene after heating to 205 °C or 320 °C. Overall, the results illustrate the utility of bench-scale treatability tests in helping to establish ISTT goals and expectations.

On the Importance of Gravity in DNAPL Invasion of Saturated Horizontal Fractures.

Invasion percolation (IP) models of dense non-aqueous phase liquid (DNAPL) invasion into saturated horizontal fractures typically neglect viscous and gravity forces, as it is assumed that capillarity dominates in many situations. An IP model simulating DNAPL invasion into saturated horizontal fractures was modified to include gravity as a local effect. The model was optimized using a genetic algorithm, and demonstrated that the inclusion of gravity is important for replicating the architecture of the DNAPL invasion pattern. The optimized gravity-included simulation showed the DNAPL invasion pattern to be significantly more representative of the experimentally observed pattern (80% accuracy) than did the optimized gravity-neglected simulation (70% accuracy). Additional simulations of DNAPL invasion in 360 randomly generated fractures were compared with and without gravity forces. These simulations showed that with increasing fracture roughness, the minimum difference between simulations with and without gravity increases to 35% for a standard deviation of the mid-aperture elevation field (SDz ) of 10 mm. Even for low roughness (SDz = 0.1 mm), the difference was as high as 30%. Furthermore, a scaled Bond Number is defined which includes data regarding DNAPL type, media type and statistical characteristics of the fracture. The value of this scaled Bond Number can be used to determine the conditions under which gravity should be considered when simulating DNAPL invasion in a macroscopically horizontal fracture. Finally, a set of equations defining the minimum and maximum absolute percentage difference between gravity-included and gravity-neglected simulations is presented based on the fracture and DNAPL characteristics.