Influence of substrate exposure history on biodegradation in a porous medium.

This study investigates the influence of fluctuating toluene concentrations on aerobic toluene degradation in a sandy porous medium colonized with Ralstonia pickettii PKO1. Column effluent toluene concentrations were found to increase after a temporary decrease in influent toluene concentration. Subsequent examination of the spatial gradient of toluene degradative activity in the column suggested that the observed increase in effluent toluene concentrations was attributable to an adverse effect of toluene limitation on the biodegradative activity of attached cells. The traditional Michaelis-Menten-type biodegradation equation associated with batch-measured Vmax (2.26 mg toluene/mg living cell/day) and KS (1.20 mg toluene/1) of nonstarved cells was unable to predict the observed toluene breakthrough behavior when the column had been previously exposed to no-toluene conditions. An alternative modeling approach was developed based upon the assumptions that (i) degradative activity was completely deactivated within the no-toluene exposure period (53.5 h) and (ii) a lag-phase was present prior to the subsequent reactivation of degradative activity in previously toluene-starved cells. These assumptions were independently verified by batch microbial investigations, and the modified model provided a good fit to the same observed toluene breakthrough curve. Application of single lag-time and threshold concentration values, however, failed to predict observed toluene breakthrough under different toluene exposure conditions. Results of this experimental and modeling investigation suggested that substrate exposure history, including the length of the starvation period and the level of substrate concentration, affected the induction of biodegradation in the porous medium.

Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 1. Experimental studies.

A matrix of batch, column and two-dimensional (2-D) box experiments was conducted to investigate the coupled effects of rate-limited solubilization and layering on the entrapment and subsequent recovery of a representative dense NAPL, tetrachloroethylene (PCE), during surfactant flushing. Batch experiments were performed to determine the equilibrium solubilization capacity of the surfactant, polyoxyethylene (20) sorbitan monooleate (Tween 80), and to measure fluid viscosity, density and interfacial tension. Results of one-dimensional column studies indicated that micellar solubilization of residual PCE was rate-limited at Darcy velocities ranging from 0.8 to 8.2 cm/h and during periods of flow interruption. Effluent concentration data were used to develop effective mass transfer coefficient (Ke) expressions that were dependent upon the Darcy velocity and duration of flow interruption. To simulate subsurface heterogeneity, 2-D boxes were packed with layers of F-70 Ottawa sand and Wurtsmith aquifer material within 20-30 mesh Ottawa sand. A 4% Tween 80 solution was then flushed through PCE-contaminated boxes at several flow velocities, with periods of flow interruption. Effluent concentration data and visual observations indicated that both rate-limited solubilization and pooling of PCE above the fine layers reduced PCE recovery to levels below those anticipated from batch and column measurements. These experimental results demonstrate the potential impact of both mass transfer limitations and subsurface layering on the recovery of PCE during surfactant enhanced aquifer remediation.

Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 2. Numerical simulation.

A numerical model of surfactant enhanced solubilization was developed and applied to the simulation of nonaqueous phase liquid recovery in two-dimensional heterogeneous laboratory sand tank systems. Model parameters were derived from independent, small-scale, batch and column experiments. These parameters included viscosity, density, solubilization capacity, surfactant sorption, interfacial tension, permeability, capillary retention functions, and interphase mass transfer correlations. Model predictive capability was assessed for the evaluation of the micellar solubilization of tetrachloroethylene (PCE) in the two-dimensional systems. Predicted effluent concentrations and mass recovery agreed reasonably well with measured values. Accurate prediction of enhanced solubilization behavior in the sand tanks was found to require the incorporation of pore-scale, system-dependent, interphase mass transfer limitations, including an explicit representation of specific interfacial contact area. Predicted effluent concentrations and mass recovery were also found to depend strongly upon the initial NAPL entrapment configuration. Numerical results collectively indicate that enhanced solubilization processes in heterogeneous, laboratory sand tank systems can be successfully simulated using independently measured soil parameters and column-measured mass transfer coefficients, provided that permeability and NAPL distributions are accurately known. This implies that the accuracy of model predictions at the field scale will be constrained by our ability to quantify soil heterogeneity and NAPL distribution.

Experimental investigations of the entrapment and persistence of organic liquid contaminants in the subsurface environment.

Organic liquids are common polluters of the subsurface environment. Once released, these nonaqueous phase liquids (NAPLs) tend to become entrapped within soils and geologic formations where they may serve as long-term contaminant reservoirs. The interphase mass transfer from such entrapped residuals will ultimately control environmental exposure levels as well as the persistence and/or remedial recovery of these contaminants in the subsurface. This paper summarizes National Institute of Environmental Health Sciences-sponsored research designed to investigate and quantify NAPL entrapment and interphase mass transfer in natural porous media. Results of soil column and batch experiments are presented that highlight research findings over the past several years. These experiments explore dissolution and volatilization of hydrocarbons and chlorinated solvents in sandy porous media. Initial concentration levels and long-term recovery rates are shown to depend on fluid flow rate, soil structure, NAPL composition, and soil wetting characteristics. These observations are explained in the context of conceptual models that describe entrapped NAPL morphology and boundary layer transport. The implications of these laboratory findings on the subsurface persistence and recovery of entrapped NAPLs are discussed.

Mathematical modeling of BTX: biotransformation and transport in the subsurface.

A two-dimensional compositional model is presented; this model describes the transport and biotransformation of organic contaminants in a variably saturated subsurface environment. Modeled processes included mass exchange between constituent phases (water, air, soil, and organisms), advective and dispersive fluxes in the water phase, diffusive flux in the air phase, and biotransformation and biomass production in the biophase. In this model, solute transfer across air/water and water/solid interfaces is modeled using equilibrium relationships. Rate-limited mass transfer between the water and biophases is described with a linear driving force expression. Microbial degradation and biomass net growth are modeled by Monod-type kinetics. Solute transport and microbial growth equations are solved using an iterative Galerkin finite element method with a variable time-weighting scheme. Coupled biophase mass balance equations for each component are solved with a Newton-Raphson iterative scheme. Model capabilities are illustrated with two-dimensional, cross-sectional simulations of natural bioattenuation. The influence of biotransformation processes on the transport and extent of a toluene plume is examined.

Modeling multiphase migration of organic chemicals in groundwater systems--a review and assessment.

Over the past two decades, a number of models have been developed to describe the multiphase migration of organic chemicals in the subsurface. This paper presents the state-of-the-art with regard to such modeling efforts. The mathematical foundations of these models are explored and individual models are presented and discussed. Models are divided into three groups: a) those that assume a sharp interface between the migrating fluids; b) those that incorporate capillarity; and c) those that consider interphase transport of mass. Strengths and weaknesses of each approach are considered along with supporting data for model validation. Future research directions are also highlighted.