Removal of PCB-DNAPL from a rough-walled fracture using alcohol/polymer flooding

Phase behaviour experiments employing PCB (Aroclor 1242)/alcohol/water systems were conducted with ethanol (EtOH) and n-propanol (nPA). Both exhibited an affinity for the aqueous phase within the entire two-phase region. As much as 88% by volume (88% vol.) EtOH and 80% vol. nPA were necessary to achieve full miscibility of the PCB in the aqueous phase. DNAPL-water interfacial tension (IFT) was reduced from 38.9 dyn/cm to 4.7 dyn/cm and 2.4 dyn/cm with 80% vol. EtOH and 76% vol. nPA. The addition of alcohol brought about 41% and 54% reductions in DNAPL viscosity at maximal concentrations of EtOH and nPA. Density of the PCB-DNAPL was relatively unaffected by the presence of alcohol. A series of seven experiments were conducted where successive slugs of nPA and xanthan gum polymer solutions were injected into a fractured shale sample. A 30% vol. nPA solution injected under a hydraulic gradient of 0.36 allowed enhanced PCB removal primarily through reduction of IFT and resulted in 72% DNAPL recovery. Several pore volumes of alcohol solution were necessary to displace all the potentially mobile non-wetting phase since the high-viscosity DNAPL was mobilized at a lower flow rate than the overall fluid velocity, illustrating non-piston displacement. The injection of a 95% vol. nPA alcohol solution, theoretically at a sufficient concentration to produce fully miscible displacement of the residual DNAPL at equilibrium, resulted in non-equilibrium partitioning of the PCB into the flushing solution, likely due to the high fluid velocities in the fracture. The injection of 200 pore volumes of 95% vol. nPA solution resulted in 94% DNAPL recovery. Alcohol floods operated below the miscibility envelope appear to be a valuable source zone remedial alternative where the objective is to reduce DNAPL mobility to zero, but it should be noted that DNAPL mobility is increased during the application of the technology and steps may need to be taken to prevent unwanted vertical mobilization.     

The influence of high initial concentration aqueous-phase TCE on the performance of iron wall systems

Flow-through column tests were conducted to investigate the performance of iron wall remediation systems for the degradation of aqueous-phase trichloroethylene (TCE). Concentration profiles under steady-state transport conditions were generated by measuring TCE concentrations at sample ports located at various locations along the length of the column. The results indicated that a pseudo-first-order model is adequate at describing degradation kinetics for low initial TCE concentrations, but not for higher initial concentrations. The deviation from pseudo-first-order kinetics can be explained by interspecies competition for reactive sites between TCE and a dominant reaction product. A modification of the pseudo-first-order model that accounts for product interference predicts laboratory data for high initial concentration profiles, but deviates slightly as initial concentrations approach the solubility of TCE. The data clearly demonstrate the importance of accurately describing reaction kinetics for the purpose of designing iron wall treatment systems.     

Manipulation of density and viscosity for the optimization of DNAPL recovery by alcohol flooding

Laboratory experiments demonstrate that in situ recovery of pooled tetrachloroethene (PCE) from porous media may be accomplished more efficiently using multiple-step alcohol floods than with single alcohol floods. To optimize flooding efficiency while maintaining a low risk of downward DNAPL mobilization, a three-step flooding process is developed employing an isobutanol preflood, a composite alcohol mainflood, and a polymer solution postflood. The density and viscosity of these solutions are manipulated to prevent the onset and propagation of viscous and gravitational fingers, while maintaining phase behavior critical for efficient miscible NAPL displacement. An aqueous partitioning preflood solution of 10% by volume (10% v) isobutanol reduces the NAPL density in situ to approximately 1.00 g/ml by swelling the NAPL prior to miscible displacement induced by the mainflood. The composite alcohol mainflood, containing 65% v ethylene glycol and 35% v 1-propanol maintains miscibility while achieving neutral buoyancy and near stable displacement of the NAPL. Aqueous solutions of xanthan gum polymer efficiently displace the mainflood, reducing viscous fingering associated with waterfloods. Two-dimensional experiments using the multiple-step technique achieve 99.8% DNAPL mass recovery using a total of 0.45 pore volumes of alcohol, illustrating greater recovery efficiency than previous alcohol flooding formulations under comparable conditions.     

Relative velocities of DNAPL and aqueous phase plume migration

Numerical simulation is used to examine the relative velocities of DNAPL and aqueous phase plumes in sandy aquifers where lateral spreading of DNAPL has occurred at the base of the aquifer. The scenario being modeled is one where a permeable aquifer is underlain by a sloping aquitard, which results in lateral migration of the DNAPL down the slope, in addition to lateral migration of an aqueous phase plume subject to a specified hydraulic gradient. A sensitivity analysis is presented to the impacts of both DNAPL properties and geologic properties. The most important chemical properties governing the relative velocities of the DNAPL and the shallow aqueous phase plume are the DNAPL viscosity and the aqueous component soil-water partition coefficient (Kd). The dip of the underlying aquitard was found to be relatively unimportant, at least for the range of values studied. The scenario under consideration can be important in conceptual model development and remedial design, as in certain cases DNAPL could be migrating in areas without the evidence of a well-developed aqueous phase plume. The implication of this work is that the absence of a shallow aqueous phase plume directly downgradient of a DNAPL source zone does not rule out the possibility of deep occurrences of DNAPL beyond the shallow monitoring well network. A further finding of this study is that the occurrence of a highly sorbing compound in groundwater at virtually any concentration may indicate the immediate upgradient presence of residual or pooled DNAPL.     

Observation of trapped gas during electrical resistance heating of trichloroethylene under passive venting conditions

A two-dimensional experiment employing a heterogeneous sand pack incorporating two pools of trichloroethylene (TCE) was performed to assess the efficacy of electrical resistance heating (ERH) under passive venting conditions. Temperature monitoring displayed the existence of a TCE-water co-boiling plateau at 73.4°C, followed by continued heating to 100°C. A 5cm thick gas accumulation formed beneath a fine-grained capillary barrier during and after co-boiling. The capillary barrier did not desaturate during the course of the experiment; the only pathway for gas escape being through perforated wells traversing the barrier. The thickness of the accumulation was dictated by the entry pressure of the perforated well. The theoretical maximum TCE soil concentration within the region of gas accumulation, following gas collapse, was estimated to be 888mg/kg. Post-heating soil sampling revealed TCE concentrations in this region ranging from 27mg/kg to 96.7mg/kg, indicating removal of aqueous and gas phase TCE following co-boiling as a result of subsequent boiling of water. The equilibrium concentrations of TCE in water corresponding to the range of post-treatment concentrations in soil (6.11mg/kg to 136mg/kg) are calculated to range from 19.8mg/l to 440mg/l. The results of this experiment illustrate the importance of providing gas phase venting during the application of ERH in heterogeneous porous media.     

Multiphase flow and transport through fractured heterogeneous porous media

The migration of Dense, Non-Aqueous Phase Liquid (DNAPL) and dissolved phase contamination through a fractured heterogeneous porous medium has been investigated through the use of a multiphase compositional model. The sensitivity of the timescales of migration and the distribution of contaminant in the subsurface to the mean permeability, the variance of the permeability, and the degree of fracturing of the domain were examined. It was found that increasing the mean permeability of the domain allowed the DNAPL to penetrate deeper into the subsurface, while decreasing the mean permeability caused the DNAPL to pool at shallower depths. The presence of fractures within the system was found to control the infiltration only in the most fractured domain. Moment analysis of the nonwetting phase showed that large-scale movement had ceased after approximately 9 years (maximum duration of the source-on condition was approximately 4.5 years). This tended to be due to a redistribution of the DNAPL towards a residual configuration, as was evidenced by the gradual trending of average nonwetting phase saturations within the domain to a static value. The dissolved phase plume was found to migrate at essentially the same rate as the nonwetting phase, due to the reduced relative permeability of lenses containing DNAPL, and due to diffusive losses of mass to the matrix of fractured clay and silty-clay lenses. Some exceptions to this were found when the DNAPL could not overcome the displacement pressure of a lens, and could not by-pass the lens due to the lack of available driving force after the source had been shut off.     

Multidimensional validation of a numerical model for simulating a DNAPL release in heterogeneous porous media

A fixed-volume release of 1,2-DCE, tracked in space and time with a light transmission/image analysis system, provided a data set for the infiltration, redistribution, and immobilisation of a dense non-aqueous phase liquid (DNAPL) in a heterogeneous porous medium. The two-dimensional bench scale flow cell was packed with a spatially correlated, random heterogeneous distribution of six sand types. In order to provide the necessary modelling parameters, detailed constitutive relationships were measured at the local scale for the six sands. These experiments revealed that nonwetting phase (NWP) relative permeability-saturation (k(rN)-S(W)) relationships are strongly correlated to sand type. Trends in the best-fit k(rN)-S(W) parameters reflected a positive correlation between mean grain diameter and the maximum NWP relative permeability, k(rN)(max). Multiphase flow simulations of the bench scale experiment best reproduced the experimental observations, producing excellent matches in both time and space, when the measured, correlated local scale k(rN)-S(W) relationships were employed.     

Formation and stability of polychlorinated biphenyl Pickering emulsions

An emulsion stabilized by colloidal suspensions of finely divided solids is known as a Pickering emulsion. The potential for polychlorinated biphenyls (PCBs) to form Pickering emulsions ex situ when in contact with powdered solids, such as clays and metal oxides, is investigated here. Bentonite, iron oxide and magnesium oxide dispersions proved to be robust Pickering emulsion stabilizers, whereas manganese oxide dispersions were not. Batch experiments revealed that emulsions can be formed using a moderately low energy input and can be stabilized with solid concentrations as low as 0.5 wt.%. For the base conditions (volumetric oil fraction (phi(oil))=30 vol.%; solid concentration (chi)=2 wt.%), the formed emulsions were indefinitely stable and the initial average droplet diameters varied from 80 to 258 mum, depending on the solid used in the colloidal dispersion. The average droplet size varied at early time, but for most conditions stabilized to a steady-state value 1 week after preparation. The effect of Ostwald ripening was limited. At greater than 0.5 wt.% concentration, the efficiency of the solid dispersion as a stabilizer was dependant on the volumetric oil fraction but not on the solid concentration. Generally, systems with volumetric oil fractions outside of the 20-70 vol.% range were unstable. The emulsions' droplet stability, average droplet size and size distribution were observed to vary as a function of the amount of energy provided to the system, the volumetric oil fraction, and the concentration of the solid in the aqueous dispersion. It is hypothesized that drilling through fractured rock in the immediate vicinity of dense, non-aqueous phase liquid (DNAPL) PCBs may provide both the energy and solid material necessary to form Pickering emulsions.     

Multiphase flow and transport in fractured clay/sand sequences.

A numerical model (Queen's University Multi-Phase Flow Simulator, QUMPFS) was used to assess the rate of trichloroethylene (TCE) dense, non-aqueous phase liquid (DNAPL) migration through fractured clay, with special attention focused on the influence of interbedded sand lenses. The presence of these sand lenses was found to increase the time required for the non-wetting phase to migrate through the full 30 m vertical extent of the clay sequence from a few days to several years. Applied vertical hydraulic gradients were found to be moderately influential in systems consisting solely of fractured clays, yet one of the dominant factors controlling speed of vertical migration when sand lenses were present. Larger displacement pressure of the sands relative to that of the fractures leads to slower DNAPL migration rates, due to the delays that occur during build-up of capillary pressures. Dissolution of DNAPL and subsequent matrix diffusion of the aqueous phase has little effect on the rate of DNAPL migration through systems consisting of fractured clay only, yet slows the rate of migration in systems containing sand lenses. In all cases examined, the rate of DNAPL loading to the lower aquifer far exceeded the rate of aqueous phase mass loading. It was also found that DNAPL reaches the lower aquifer at approximately the same time as the aqueous phase plumes even for systems experiencing downward groundwater flow due to the attenuation of the aqueous phase through matrix diffusion.