A 13-year study of tritium transport through a field-scale earthen liner was conducted by the Illinois State Geological Survey to determine the long-term performance of compacted soil liners in limiting chemical transport. Two field-sampling procedures (pressure-vacuum lysimeter and core sampling) were used to determine the vertical tritium concentration profiles at different times and locations within the liner. Profiles determined by the two methods were similar and consistent. Analyses of the concentration profiles showed that the tritium concentration was relatively uniformly distributed horizontally at each sampling depth within the liner and thus there was no apparent preferential transport. A simple one-dimensional analytical solution to the advective–dispersive solute transport equation was used to model tritium transport through the liner. Modeling results showed that diffusion was the dominant contaminant transport mechanism. The measured tritium concentration profiles were accurately modeled with an effective diffusion coefficient of 6×10−4mm2/s, which is in the middle of the range of values reported in the literature.
Magnetic resonance imaging (MRI) was used to determine the effects of pore-scale heterogeneity on the dissolution of a nonaqueous phase liquid (NAPL) in water-saturated flow-through columns (1.2 cm in diameter) packed with either ∼500 or ∼1000 micron diameter angular silica gel (referred to as SG500 and SG1000, respectively). Columns were contaminated with 1,3,5-trifluorobenzene at residual saturation and then purged with water at a constant Darcy velocity of 1.83 m/day. Three-dimensional 19F images were acquired every 2−5 h at an imaging resolution of 59 × 234 × 234 μm3. Imaging results show that the specific NAPL surface area (at) is linearly related to the NAPL volumetric fraction (θn) and that the constant of proportionality between these parameters is determined by the blob size and geometry distribution. Overall (expressed as the modified Sherwood number, Sh') and intrinsic (expressed as the apparent Sherwood number, Shapt) mass transfer rate coefficients were calculated. Values of Sh' and Shapt for SG500 were approximately three times less than those for SG1000. For both solids, Sh' first increased or stayed the same and then decreased with decreasing θn, while Shapt generally increased with decreasing θn. These results suggest that during dissolution new flow paths were created (i.e., bypass zones were eliminated) as NAPL dissolved, decreasing the fraction of NAPL−water interfaces adjacent to pores filled with stagnant water and the average diffusion length scale. Since at for SG500 was dominated by less spherical multipore blobs (as opposed to more spherical singlets for SG1000), these results also suggest that the extent of flow bypassing (and the average diffusion length scale) increases in systems with more irregular blobs. These results are important because Sh' correlations and a “sphere” dissolution model do not account for transient changes in the fraction of NAPL surface area that contributes to dissolution or for the effect of initial blob size and geometry distribution on this fraction.
Parameters from single‐component isotherm models were used in multicomponent isotherm models to predict the aqueous phase sorption of trichloroethylene (TCE) in the presence of tetrachloroethylene (PCE) in four zeolites, Tenax, and three natural solids. The Langmuir, the Polanyi‐Dubinin, and the Freundlich or the Langmuir‐Freundlich isotherm models were used to simulate single‐component sorption in zeolites. The Langmuir two‐site, the Polanyi‐Dubinin two‐site, and the Freundlich or the Langmuir‐Freundlich isotherm models were used to simulate single‐component sorption in Tenax and natural solids. Two‐site models have been used previously to model sorption in soils and sediments, and they combine an adsorption component (e.g., Langmuir) with a linear partitioning component. By using parameters from the different single‐component isotherm models, the multicomponent Langmuir, the ideal adsorbed solution theory, and the Polanyi theory were each used to predict multicomponent sorption. In general, the ability to predict TCE sorption in the presence of PCE depended more on the choice of the single‐component model than the multicomponent model, and better results were obtained when the Freundlich or the Langmuir‐Freundlich isotherm was used for single‐component sorption. This suggests that the more mechanistically based Langmuir and Polanyi‐type models may not adequately describe the distribution of adsorption sites in some model and natural solids. The Freundlich or the Langmuir‐Freundlich model, although empirical, has greater flexibility in characterizing sorbent heterogeneity and results in better multicomponent model predictions. However, this last statement is tenuous, because more solids must be tested against various model combinations.
The competitive sorption of trichloroethene (TCE) and tetrachloroethene (PCE) was investigated in three natural solids, two polymers, and four zeolites. Competition was observed in natural solids with high contents of recalcitrant organic carbon, in the glassy polymer, and in zeolites with strongly and moderately hydrophobic micropores of large (7.5 × 10 Å) and small pore widths (∼5.4 Å), respectively. Isotherm results and recalcitrant OC% values for natural solids indicate that the extent of competition between TCE and PCE is related to the amount of hard organic carbon. Gas adsorption results and the variability in C/H values suggest that natural organic matter contains micropores with varying width and polarity. Isotherm results for zeolites indicate that competition between TCE and PCE increases with increasing hydrophobicity and decreasing micropore width. We suggest that competition between volatile organic contaminants in the subsurface is controlled by competition for hydrophobic micropores in hard organic matter and that smaller more hydrophobic micropores result in stronger competition.
Contamination of groundwater by nonaqueous phase liquids (NAPLs) is widely recognized as a serious environmental problem. Predicting the dissolution, fate, and transport of these organic chemicals in the subsurface is challenging because geological heterogeneity exists at numerous scales. To better understand heterogeneity at the pore scale, we use the lattice Boltzmann (LB) method to simulate water flow and solute transport from distributed NAPL blobs in a two‐dimensional porous media. The LB method approximates the momentum and mass transport equations at the pore scale, easily incorporating complex boundary conditions of the porous media. The effects of NAPL blob configuration and Peclet number (Pe) on steady state mass transfer are studied at 7% and 15% NAPL saturation. We find that the solute flux out of the simulated system decreases substantially as the transverse length over which NAPL blobs are distributed decreases; for example, the solute flux is reduced by a factor of 2 by confining the NAPL blobs to only half of the transverse length. Values of Sherwood numbers determined from our simulations are slightly less than values determined from previously published mass transfer correlations. Our results indicate that pore‐scale NAPL configuration significantly affects mass transfer and that correlations should be modified to account for it. We find that the dimensionless mass transfer coefficient increases with Pe for the values used in our simulations, where the rate of increase decreases with increasing Pe. We observe that much of the variability in computed mass transfer coefficients is accounted for by differences in the NAPL‐water interfacial area at high Pe. However, at lower Pe, variability remains due to NAPL configuration.
Binary solute desorption isotherms of trichloroethylene (TCE) and tetrachloroethylene (PCE) at 100% relative humidity from silica gel and two well-characterized natural solids were investigated. Results indicated that the ideal adsorbed solution theory (IAST) was able to describe desorption isotherms for the silica gel. For the natural solids, IAST was not able to describe desorption isotherms for the full concentration range examined. Failure of IAST was greatest for the most heterogeneous sorbent, even when considering multiple sorption domains. In addition, IAST predictions worsened as nonlinear uptake mechanisms began to dominate. Several possible explanations for the failure of the IAST are given, including the possibility that complex interactions between the sorbing solutes and the sorbent may exist, causing deviations from ideal sorption behavior.
In the first of this two-paper series, a new model is presented that simulates the effects of a temperature perturbation on the rate of slow desorption as a function of mass remaining. The model assumes slow desorption is controlled by one-dimensional diffusion from a single or many hydrophobic micropores and that the micropores of a geosorbent are defined by a γ distribution of diffusion rate constants. Simulation results indicate that during slow desorption the relative increase in flux upon heating increases with decreasing micropore width. Simulation results also indicate that the relative increase in flux upon heating increases with desorption time when diffusion occurs from successively smaller width micropores with decreasing mass remaining. In paper 2, the model is tested and used to examine micropore geometry in natural and model solids by simulating results from temperature stepped desorption (TSD) experiments.
Results from temperature stepped desorption (TSD) experiments are presented and compared with simulations from the TSD model presented in the first of this two-paper series. TSD columns were filled with a sand, a sediment, a soil, or a silica gel, all at 100% relative humidity. Next, TSD columns were equilibrated with trichloroethene (TCE), initially purged at 30 °C, and then heated to 60 °C after 100, 1000, or 10 000 min of slow desorption. One γ distribution of diffusion rate constants at 30 °C and one γ distribution of diffusion rate constants at 60 °C were used to simulate column results at all three heating times for a single solid. At each heating time, diffusion rate constants of the γ distributions at 30 °C and 60 °C were used to calculated an effective activation energy, Eact,eff. Values of Eact,eff for all solids were between 47 and 94 kJ/mol, on the order of activation energy values found for diffusion in microporous solids. Between 100 and 10 000 min heating times, the value of Eact,eff increased by a factor of 1.7 for the sand and by a factor of ∼1.1 for the sediment and the soil. This suggests that diffusion occurs from micropores with a wider distribution of widths in the sand than in the other solids and that with decreasing mass remaining diffusion occurs from successively smaller width micropores. For the sediment, values of Eact,eff and 〈D/lm2〉 were lower than those in the other solids. For a given sorbate, larger width micropores are associated with smaller values of Eact,eff and larger values of D. Hence, it is likely that micropores in the sediment are both wider and longer (i.e. larger value of lm2) than those in the other solids. These results suggest that micropore geometry varies between natural solids, and it is an important parameter that must be quantified to predict rates of slow desorption.
In the first paper of this two‐paper series, we present a new model that attributes nonequilibrium sorption of moderately hydrophobia, volatile organic compounds to intragranular diffusion. The model differs from those of previous researchers in that for the first time, it combines the following elements: (1) We account for two distinct intragranular rate‐limiting diffusion processes, occurring in series and at widely different timescales; (2) we describe the slower of the two processes with a gamma distribution of diffusion rates; and (3) we use the disparity of timescales of the two processes to approximate a boundary condition for the distributed diffusion equation, allowing it to be solved analytically. The slower diffusion process is attributed to activated diffusion through very small pores, called micropores. In paper 2 [Werth et al., this issue] we evaluate the capabilities of the model and use it to interpret experimental results.
Trichloroethylene (TCE) elution profiles for purged and unswept columns are presented and simulated with the Distributed Dual Diffusion Model (DDDM) presented in the first of this two‐paper series. Elution profiles were measured at 15, 22, 30, and/or 60°C for a silica gel, a Livermore sand fraction, a Livermore clay and silt fraction, a Santa Clara sediment, and/or a Norwood soil, all at 100% relative humidity. Advection and dispersion control TCE transport through the vapor phase of purged columns. Diffusion controls TCE transport through the vapor phase of unswept columns. For both purged and unswept columns a fast and a slow desorbing fraction of TCE were observed. The DDDM effectively simulated both of these fractions. For the fast fraction the DDDM predicted desorption with no fitting parameters. For the slow fraction the DDDM was not predictive but it simulated desorption using either a single (for silica gel) or a gamma distribution (for soil and sediments) of micropore diffusion rate constant(s) and a micropore capacity factor. Micropore capacity factors obtained by fitting the DDDM to purged column results were used to predict the onset of slow desorption in unswept columns of the same solid.
Isothermal desorption rates were measured at 15, 30, and 60 °C for trichloroethylene (TCE) on a silica gel, an aquifer sediment, a soil, a sand fraction, and a clay and silt fraction, all at 100% relative humidity. Temperature-stepped desorption (TSD) rates were measured for these solids in columns prepared and equilibrated at 30 °C, but heated instantaneously to 60 °C after ∼1000 min of slow desorption. Fast and slow elution rates are observed for all solids. Modeling results for the fast eluting fraction of TCE show that fast desorption is controlled by diffusion through aqueous filled mesopores. Rates predicted from diffusion and surface-barrier models are compared to slow isothermal and TSD rates. Diffusion model fits are superior to surface-barrier model fits in all cases. Slow diffusion coefficients and a high activation energy calculated from silica gel data (∼34 kJ/mol) indicate that slow desorption is controlled by activated diffusion in micropores. Initial amounts of slow desorbing TCE do not affect these rates and are found to obey Polanyi's equation. The mass adsorbed in non-Freundlich isotherm regions, where micropores are hypothesized to control adsorption, is 10 times greater than the mass adsorbed at the onset of slow desorption, suggesting that these pores are undulating in nature. TSD column results are consistent with a mechanism where slow diffusion rates are controlled by sorptive forces at hydrophobic micropore constrictions.
Aqueous phase isotherms were calculated from vapor phase desorption isotherms measured at 15, 30, and 60 °C for trichloroethylene on a silica gel, an aquifer sediment, a soil, a sand fraction, and a clay and silt fraction, all at 100% relative humidity. Isosteric heats of adsorption (Qst(q)) were calculated as a function of the sorbed concentration, q, and examined with respect to the following mechanisms: adsorption on water wet mineral surfaces, sorption in amorphous organic matter (AOM), and adsorption in hydrophobic micropores. Silica gel, sand fraction, and clay and silt fraction 60 °C isotherms are characterized by a Freundlich region and a region at very low concentrations where isotherm points deviate from log-log linear behavior. The latter is designated the non-Freundlich region. For the silica gel, values of Qst(q) (9.5−45 kJ/mol) in both regions are consistent with adsorption in hydrophobic micropores. For the natural solids, values of Qst(q) in the Freundlich regions are less than or equal to zero and are consistent with sorption on water wet mineral surfaces and in AOM. In the non-Freundlich regions, diverging different temperature isotherms with decreasing q and a Qst(q) value of 34 kJ/mol for the clay and silt fraction suggest that adsorption is occurring in hydrophobic micropores. The General Adsorption Isotherm is used to capture this adsorption heterogeneity.