Electromagnetically-vibrated solid-phase microextraction for analysis of aqueous-miscible organic compound transport in soil columns.

Current methods of sampling pore water from soil columns to determine solute concentrations are slow and require relatively large volumes. Accordingly, an electromagnetically-vibrated (EMV) solid-phase microextraction (SPME) device was evaluated for determining temporal and spatial distributions of solute pore-water concentrations (solute concentration profiles) for four organic compounds, two polar (2-hexanone, 2,4-dimethyl phenol) and two nonpolar (toluene, 1,4-dichlorobenzene), in columns packed with simulated aquifer sands with different fractions of organic carbon. In batch equilibrium extraction tests, the equilibrium extraction time of the organic compounds in aqueous mixtures decreased from 30 to less than 10 min as the frequency of electromagnetic vibration increased from zero to 250 Hz. Mixture effects were not statistically significant (p > 0.05) in the extraction process using EMV SPME. Comparisons of the solute concentration profiles within the soil columns at different elapsed times measured by pore-water samples and in situ EMV SPME extractions revealed both methods were equally effective. However, EMV SPME extraction removed no solution volume and only 0.6-14% of the solute mass removed by the pore-water sample collections, substantially minimizing disturbances to solute transport and fate. Thus, the equilibrium extraction-based calibration method using EMV SPME offers an effective approach for rapidly and accurately determining solute concentration profiles in column tests with negligible solute mass loss and minimal solution flow disturbance.

Modeling sorption of neutral organic compound mixtures to simulated aquifer sorbents with pseudocompounds.

The feasibility of the ideal adsorbed solution theory (IAST) in reducing the complexity associated with predicting the sorption behaviors of 12 neutral organic compounds (NOCs) contained in complex mixtures as a fewer number (four to six) of pseudocompounds (groups of compounds) to simulated aquifer sorbents was investigated. All sorption isotherms from individual- and multiple-pseudocompound systems were fit reasonably well ( ≥ 0.953) by the Freundlich sorption model over the range of aqueous concentrations evaluated (i.e., ≤200 µmol L). The presence and magnitude of mutual competition among pseudocompounds varied depending on the composition of the mixtures (i.e., concentrations and polarities of pseudocompounds) and the properties of sorbents (i.e., the fraction of organic carbon and the availability of hydrophilic specific sorption sites). Finally, comparisons between the IAST-based predictions with individual-pseudocompound sorption parameters and experimentally measured data revealed that the accuracy in predicting the sorption behaviors of several NOCs in terms of a fewer number of pseudocompounds decreased with increasing deviations from the assumption of equal and ideal competition in the IAST (i.e., differential availability of sorption sites and nonideal competitions among pseudocompounds).

Critical review of coupled flux formulations for clay membranes based on nonequilibrium thermodynamics.

Extensive research conducted over the past several decades has indicated that semipermeable membrane behavior (i.e., the ability of a porous medium to restrict the passage of solutes) may have a significant influence on solute migration through a wide variety of clay-rich soils, including both natural clay formations (aquitards, aquicludes) and engineered clay barriers (e.g., landfill liners and vertical cutoff walls). Restricted solute migration through clay membranes generally has been described using coupled flux formulations based on nonequilibrium (irreversible) thermodynamics. However, these formulations have differed depending on the assumptions inherent in the theoretical development, resulting in some confusion regarding the applicability of the formulations. Accordingly, a critical review of coupled flux formulations for liquid, current, and solutes through a semipermeable clay membrane under isothermal conditions is undertaken with the goals of explicitly resolving differences among the formulations and illustrating the significance of the differences from theoretical and practical perspectives. Formulations based on single-solute systems (i.e., uncharged solute), single-salt systems, and general systems containing multiple cations or anions are presented. Also, expressions relating the phenomenological coefficients in the coupled flux equations to relevant soil properties (e.g., hydraulic conductivity and effective diffusion coefficient) are summarized for each system. A major difference in the formulations is shown to exist depending on whether counter diffusion or salt diffusion is assumed. This difference between counter and salt diffusion is shown to affect the interpretation of values for the effective diffusion coefficient in a clay membrane based on previously published experimental data. Solute transport theories based on both counter and salt diffusion then are used to re-evaluate previously published column test data for the same clay membrane. The results indicate that, despite the theoretical inconsistency between the counter-diffusion assumption and the salt-diffusion conditions of the experiments, the predictive ability of solute transport theory based on the assumption of counter diffusion is not significantly different from that based on the assumption of salt diffusion, provided that the input parameters used in each theory are derived under the same assumption inherent in the theory. Nonetheless, salt-diffusion theory is fundamentally correct and, therefore, is more appropriate for problems involving salt diffusion in clay membranes. Finally, the fact that solute diffusion cannot occur in an ideal or perfect membrane is not explicitly captured in any of the theoretical expressions for total solute flux in clay membranes, but rather is generally accounted for via inclusion of an effective porosity, n(e), or a restrictive tortuosity factor, τ(r), in the formulation of Fick's first law for diffusion. Both n(e) and τ(r) have been correlated as a linear function of membrane efficiency. This linear correlation is supported theoretically by pore-scale modeling of solid-liquid interactions, but experimental support is limited. Additional data are needed to bolster the validity of the linear correlation for clay membranes.

Influence of adsorption on phenol transport through soil-bentonite vertical barriers amended with activated carbon.

The potential for enhanced containment of phenol by soil-bentonite (SB) vertical barriers amended with activated carbon (AC) was investigated. Results of batch equilibrium adsorption tests on model SB backfills amended with 0-10 wt.% granular AC (GAC) or powdered AC (PAC) illustrate that the backfills exhibited nonlinear adsorption behavior that was described well by both the Freundlich and Tóth adsorption models. The AC amended backfills exhibited enhanced phenol adsorption relative to unamended backfill due to hydrophobic partitioning to the AC. Adsorption capacity increased with increasing AC content but was insensitive to AC type (GAC versus PAC). Results of numerical transport simulations based on the measured adsorption behavior show that the Tóth model yielded similar or lower phenol breakthrough times than the Freundlich model for the range of source concentrations (C(o)) considered in the simulations (0.1-10 mg/L). Breakthrough time decreased with increasing C(o) but increased with increasing AC content. Predicted breakthrough times for an SB vertical barrier amended with 2-10 wt.% AC increased by several orders of magnitude relative to the theoretical case of a nonreactive (non-adsorbing) barrier. The findings suggest that AC may be a highly effective adsorption amendment for sustaining the containment performance of SB vertical barriers.

Non-reactive solute diffusion in unconfined and confined specimens of a compacted soil.

The effect of specimen confinement on the determination of the effective diffusion coefficients, D*, for chloride, a non-reactive (non-adsorbing) solute, diffusing in a compacted soil was evaluated. The diffusion tests were performed by placing an acetic acid/sodium acetate buffer solution containing ZnCl2 (pH approximately 4.8) in a reservoir in contact with unconfined and confined specimens of a compacted sand-clay mixture for test durations of 7 or 14 d. The concentrations of chloride in the reservoir were measured as a function of time during the test, as well as a function of depth within the specimen at the end of the test. The resulting concentration distributions were analyzed using two models to Fick's second law for non-reactive solute diffusion in porous media, viz., (1) an analytical model assuming the porosity distribution could be represented by a single, weighted mean porosity and (2) a commercially available model, POLLUTE, that directly accounted for the measured porosity distribution. The D* for unconfined specimens based on the analytical model tended to be overestimated by a factor ranging from 1.13 to 1.59 relative to the D* using POLLUTE, whereas the D* values based on both methods for confined specimens typically were more consistent. In addition, the D* for unconfined specimens was greater than the D* for confined specimens when soil concentrations were used for the analysis, presumably due to the higher porosity for the unconfined specimens relative to the confined specimens. Analyses based on reservoir concentrations were inconsistent and contradictory in some cases, suggesting that the D* values based on soil concentrations were more reliable.

Association of humic acid with metal (hydr)oxide-coated sands at solid-water interfaces.

Mineral-bound humic acid (HA) can significantly modify the physicochemical properties of the mineral surfaces and vice versa, thereby influencing the fate and transport of organic pollutants in the subsurface. The effect of various mineral surfaces on the adsorption-desorption of dissolved bulk, terrestrial HA was evaluated using three model sorbents [uncoated, alpha-FeO(OH)-coated, and Al2O3-coated sands] at two equilibrium pH values. The results of SEM/EDS and XPS analyses revealed relatively uniform and stable metal (hydr)oxide coatings on quartz surface and the presence of the HA coating. Strong hysteresis effects were observed for both metal (hydr)oxide-coated sands whereas a weaker hysteresis effect was observed for uncoated sand, suggesting that the adsorption-desorption of HA to model sorbents is dependent on the affinity of chemical interactions between the HA and surface composition of model sorbents. Adsorption of HA molecules onto metal (hydr)oxide-coated sands can be attributed to ligand exchange for lower molecular weight (MW) HA fractions and hydrophobic interaction for higher MW HA fractions, illustrating that both kinetic and fractional adsorption-desorption of HA subcomponents are important considerations.

Sorption of nonpolar neutral organic compounds to humic acid-coated sands: contributions of organic and mineral components.

The contributions of organic matter and the mineral surface to the overall sorption of six nonpolar neutral organic compounds (1,2,4-trichlorobenzene, 1,4-dichlorobenzene, chlorobenzene, m-xylene, toluene, benzene) by five humic acid (HA)-coated sands with different fractions of organic carbon (f(oc)) ranging from 0.024% to 0.154% were evaluated on the basis of measured data and four different sorption models. Sorption of all six sorbates to both uncoated and heated sands was nearly linear due to the coverage of hydrophilic mineral surface with the ordered vicinal water region. Sorption of all six sorbates to the HA-coated sands was also essentially linear, and resulted from a combination of sorption to both organic matter and the mineral surface, with the dominance of either contribution depending on the properties of the sorbents (e.g., f(oc)) and the sorbates (e.g., K(ow)). A proposed two-component model for sorption including blocking effect was appropriate for quantifying the contributions of organic matter and the mineral surface to the overall sorption. However, conventional sorption models considering the contributions of both organic matter and the mineral surface provided essentially as good agreement between predicted and measured distribution coefficients as the more complicated, two-component model for sorption that takes into account mineral surface blocking by HA.

Modeling the influence of decomposing organic solids on sulfate reduction rates for iron precipitation.

The influence of decomposing organic solids on sulfate (S04(2-)) reduction rates for metals precipitation in sulfate-reducing systems, such as in bioreactors and permeable reactive barriers for treatment of acid mine drainage, is modeled. The results are evaluated by comparing the model simulations with published experimental data for two single-substrate and two multiple-substrate batch equilibrium experiments. The comparisons are based on the temporal trends in SO4(2-), ferrous iron (Fe2+), and hydrogen sulfide (H2S) concentrations, as well as on rates of sulfate reduction. The temporal behaviors of organic solid materials, dissolved organic substrates, and different bacterial populations also are simulated. The simulated results using Contois kinetics for polysaccharide decomposition, Monod kinetics for lactate-based sulfate reduction, instantaneous or kinetically controlled precipitation of ferrous iron mono-sulfide (FeS), and partial volatilization of H2S to the gas phase compare favorably with the experimental data. When Contois kinetics of polysaccharide decomposition is replaced by first-order kinetics to simulate one of the single-substrate batch experiments, a comparatively poorer approximation of the rates of sulfate reduction is obtained. The effect of sewage sludge in boosting the short-term rate of sulfate reduction in one of the multiple-substrate experiments also is approximated reasonably well. The results illustrate the importance of the type of kinetics used to describe the decomposition of organic solids on metals precipitation in sulfate-reducing systems as well as the potential application of the model as a predictive tool for assisting in the design of similar biochemical systems.

Explicit and implicit coupling during solute transport through clay membrane barriers.

Simulations of salt (KCl) flux through a 1-m-thick clay membrane barrier (CMB) based on coupled solute transport theory are compared to simulated fluxes based on traditional advective-dispersive transport theory. The simulations are based on measured values for the effective salt-diffusion coefficient (Ds*) and chemico-osmotic efficiency coefficient (omega) for a bentonite-based barrier material subjected to KCl solutions. The results indicate that the exit salt flux is reduced due to both explicit coupling (hyperfiltration and chemico-osmotic counter-advection) and an implicit coupling effect resulting from the decrease in Ds* due to a decrease in the apparent tortuosity factor, tau a, with an increase in omega. Implicit coupling is shown to be more significant than explicit coupling for reducing and retarding salt flux through a CMB under diffusion-dominated conditions. Failure to account for the implicit coupling effect may result in unrealistic results, such as the existence of salt flux through a perfect (ideal) clay membrane (i.e., omega=1).

Theory for reactive solute transport through clay membrane barriers.

The theoretical development for one-dimensional, coupled migration of solutes with different ionic mobilities through clay soils that behave as ion-restrictive membranes, referred to as clay membrane barriers (CMBs), is presented. The transport formulation is based on principles of irreversible thermodynamics and accounts explicitly for coupling effects of hyperfiltration (ultrafiltration) and chemico-osmotic counter-advection associated with clay membrane behavior in the absence of electrical current. Since, by definition, no solute can enter a "perfect" or "ideal" membrane, the concept of an implicit coupling effect, such that the effective salt-diffusion coefficient, Ds* approaches zero as the chemico-osmotic efficiency coefficient, omega approaches unity is introduced. The theoretical development also illustrates that, even in the absence of membrane behavior, traditional advective-dispersive transport theory based on a constant value of Ds* for the solutes may not be appropriate for simulating transient transport in reactive (ion exchanging) systems. This potential limitation is illustrated through simulations for solute mass flux involving the migration of a binary salt solution (KCl) through a clay barrier with exchange sites saturated with a single exchangeable cation (e.g., Na+) that enters the pore solution upon ion exchange with the salt cation (K+).

Coupling effects during steady-state solute diffusion through a semipermeable clay membrane.

Two separate coupling effects are evaluated with respect to steady-state potassium chloride (KCl) diffusion through a bentonite-based geosynthetic clay liner (GCL) that behaves as a semipermeable membrane. Both of the coupling effects are correlated with measured chemico-osmotic efficiency coefficients, omega, that range from 0.14 to 0.63 for the GCL. The first coupling effect is an explicit (theoretical) salt-sieving effect expressed as a coupled effective salt diffusion coefficient, Domega*, that is lower than the true (uncoupled) effective salt diffusion coefficient, Ds*, because of the observed membrane behavior. However, the maximum difference between Domega* and Ds* based on measured chloride concentrations is relatively small (i.e., = 10%), and the difference decreases with decreasing omega (i.e., Domega* --> Ds* as omega --> 0). The second coupling effect is implicit (empirical) and is characterized by the measurement of concentration-dependent effective salt diffusion coefficients that results in an degrees 300% decrease in Ds* as omega increases from 0.14 to 0.63. The decrease in Ds* resulting from implicit coupling is attributed to solute exclusion described in terms of a restrictive tortuosity factor.