UNIFAC Modeling of Cosolvent Phase Partitioning in Nonaqueous Phase Liquid-Water Systems

In this study, an existing thermodynamic model was used to predict equilibrium phase partitioning behavior of a cosolvent in a two-phase nonaqueous phase liquid (NAPL)–water system. The activity coefficients are calculated using the universal quasichemical functional group activity coefficient (UNIFAC) method. We examined an assortment of cosolvent–NAPL pairs of environmental interest and compared the UNIFAC-predicted ternary phase diagrams against published experimentally derived ternary phase diagrams. Results show that the UNIFAC model is a promising method for predicting equilibrium cosolvent partitioning behavior in NAPL–water systems, and thus can be useful in estimating the potential for NAPL solubilization and mobilization in remediation processes. The cosolvent partitioning behavior is interpreted with regard to changes in the physical properties of the NAPL-water system. Changes in interfacial tension between the two phases were estimated using an existing correlation. A viscosity experiment was conducted for selected mixtures of ethanol, toluene, and water; and the viscosity was found to increase with increasing amounts of the cosolvent.     

Preferential Flow of a Nonaqueous Phase Liquid in Dry Sand

Geotechnical centrifuge testing is used to examine the preferential (fingered) flow of a nonaqueous phase liquid (NAPL) in a uniform dry sand. The results of nine experiments, containing a total of 87 observations of NAPL finger behavior, are analyzed. The observed finger tip velocities range from 0.01 to 0.3 cm/s, while the observed finger widths range from 0.3 to 3.6 cm. From the experimental data it is concluded that, asymptotically, the NAPL fingers are not fully saturated. For comparison, the behavior of water fingers is examined using the same experimental setup. In contrast to the NAPL fingers, and in agreement with other work reported in the literature, the water fingers are found to be fully saturated. In addition, it is confirmed that the water finger properties can be well predicted from known porous medium and fluid properties. A scaling analysis is presented that allows the NAPL finger properties to be inferred from models developed to describe water finger properties. The analysis predicts NAPL finger velocities to within 15% and NAPL finger widths to within 50% if both finger types are assumed saturated. By adjusting the analysis to account for the fact that the NAPL fingers are not fully saturated, NAPL finger widths can be predicted within to 10%, and NAPL finger velocities to within 30%.     

Retardation of Nonlinearly Sorbed Solutes in Porous Media

The impact of the assumption of linear sorption on retardation of nonlinearly sorbed solutes in porous media is numerically explored in this paper. Breakthrough data of nonlinearly sorbed solutes are generated using the BIO1D simulation code along with the Freundlich-type nonlinear sorption model. Retardation coefficients (R) from generated breakthrough curves are estimated using first-moment analysis. Variations of R with experimental conditions revealed that R of a nonlinearly sorbed solute is a function of the input concentration, the injection period and the pore-water velocity but is independent of the length scale. This study also showed that it is appropriate to estimate R of a nonlinearly sorbed solute using a linearized isotherm if all soil particles experience sorption with liquid concentration equal to the induced concentration. Otherwise, the estimated linearized R will be either under- or overestimated depending on the applied experimental conditions and Freundlich parameters. The study further revealed that inability to account for sorption nonlinearity may in some cases erroneously be interpreted as evidence of the presence of transport nonequilibrium. A method is suggested to determine nonlinear sorption parameters from miscible displacement experiments.     

Nonaqueous Phase Liquid Pool Dissolution as a Function of Average Pore Water Velocity

Bench-scale reactor experiments were performed to study the dissolution of a binary naphthalene-in-nonane mixture nonaqueous phase liquid (NAPL) pool over a wide range of average pore water velocities, vx (≈0.1–60 m/day). Experimental NAPL pool dissolution flux values were determined using a steady-state mass balance approach. The experimental flux data were compared to model predictions made assuming either local equilibrium or mass-transfer limited conditions. The local equilibrium model could describe the trends in the average effluent concentration and dissolution flux with 0.110?m/day. Data determined to be under mass-transfer limited conditions were fit to the nonequilibrium model to estimate values for an overall mass-transfer coefficient. The calculated overall mass-transfer coefficients had an average value of 0.407 m/day and showed no correlation with vx, probably due to mass-transfer resistance becoming dominated by the diffusional resistance in the NAPL. These results suggest that the nonequilibrium approach is better suited for describing high velocity (vx>10?m/day) dissolution of multicomponent NAPL pools, and that flushing of groundwater at very high velocities may not be an effective approach for enhancing NAPL-pool dissolution flux.     

Retardation of Nonlinearly Sorbed Solutes in Porous Media

The impact of the assumption of linear sorption on retardation of nonlinearly sorbed solutes in porous media is numerically explored in this paper. Breakthrough data of nonlinearly sorbed solutes are generated using the BIO1D simulation code along with the Freundlich-type nonlinear sorption model. Retardation coefficients (R) from generated breakthrough curves are estimated using first-moment analysis. Variations of R with experimental conditions revealed that R of a nonlinearly sorbed solute is a function of the input concentration, the injection period, and the pore–water velocity but is independent of the length scale. This study also showed that it is appropriate to estimate R of a nonlinearly sorbed solute using a linearized isotherm if all soil particles experience sorption with liquid concentration equal to the induced concentration. Otherwise, the estimated linearized R will be either under- or overestimated depending on the applied experimental conditions and Freundlich parameters. The study further revealed that inability to account for sorption nonlinearity may in some cases erroneously be interpreted as evidence of the presence of transport nonequilibrium. A method is suggested to determine nonlinear sorption parameters from miscible displacement experiments.     

Destruction of a Carbon Tetrachloride Dense Nonaqueous Phase Liquid by Modified Fenton’s Reagent

Destruction of a dense nonaqueous phase liquid (DNAPL) by soluble iron (III)-catalyzed and pyrolusite (β-MnO2)-catalyzed Fenton’s reactions (hydrogen peroxide and transition metal catalysts) was investigated using carbon tetrachloride (CT) as a model contaminant. In the system amended with 5 mM soluble iron (III), 24% of the CT DNAPL was destroyed after 3 h while CT dissolution in parallel fill-and-draw systems was minimal, indicating that CT was degraded more rapidly than it dissolved into the aqueous phase. Fenton’s reactions catalyzed by the naturally occurring manganese oxide pyrolusite were even more effective in destroying CT DNAPLs, with 53% degradation after 3 h. Although Fenton’s reactions are characterized by hydroxyl radical generation, carbon tetrachloride is unreactive with hydroxyl radicals; therefore, a transient oxygen species other than hydroxyl radicals formed through Fenton’s propagation reactions was likely responsible for CT destruction. These results demonstrate that Fenton-like reactions in which nonhydroxyl radical species are generated may provide an effective method for the in situ treatment of DNAPLs.