A novel two-dimensional model for colloid transport in physically and geochemically heterogeneous porous media

A two-dimensional model for colloid transport in geochemically and physically heterogeneous porous media is presented. The model considers patchwise geochemical heterogeneity, which is suitable to describe the chemical variability of many surficial aquifers with ferric oxyhydroxide-coated porous matrix, as well as spatial variability of hydraulic conductivity, which results in heterogeneous flow field. The model is comprised of a transient fluid flow equation, a transient colloid transport equation, and an equation for the dynamics of colloid deposition and release. Numerical simulations were carried out with the model to investigate the colloid transport behavior in layered and randomly heterogeneous porous media. Results demonstrate that physical and geochemical heterogeneities markedly affect the colloid transport behavior. Layered physical or geochemical heterogeneity can result in distinct preferential flow paths of colloidal particles. Furthermore, the combined effect of layered physical and geochemical heterogeneity may result in enhanced or reduced preferential flow of colloids. Random distribution of physical heterogeneity (hydraulic conductivity) results in a random flow field and an irregularly distributed colloid concentration profile in the porous medium. Contrary to random physical heterogeneity, the effect of random patchwise geochemical heterogeneity on colloid transport behavior is not significant. It is mostly the mean value of geochemical heterogeneity rather than its distribution that governs the colloid transport behavior.     

Biodegradation during contaminant transport in porous media: 4. Impact of microbial lag and bacterial cell growth

Miscible-displacement experiments were conducted to examine the impact of microbial lag and bacterial cell growth on the transport of salicylate, a model hydrocarbon compound. The impacts of these processes were examined separately, as well as jointly, to determine their relative effects on biodegradation dynamics. For each experiment, a column was packed with porous medium that was first inoculated with bacteria that contained the NAH plasmid encoding genes for the degradation of naphthalene and salicylate, and then subjected to a step input of salicylate solution. The transport behavior of salicylate was non-steady for all cases examined, and was clearly influenced by a delay (lag) in the onset of biodegradation. This microbial lag, which was consistent with the results of batch experiments, is attributed to the induction and synthesis of the enzymes required for biodegradation of salicylate. The effect of microbial lag on salicylate transport was eliminated by exposing the column to two successive pulses of salicylate, thereby allowing the cells to acclimate to the carbon source during the first pulse. Elimination of microbial lag effects allowed the impact of bacterial growth on salicylate transport to be quantified, which was accomplished by determining a cell mass balance. Conversely, the impact of microbial lag was further investigated by performing a similar double-pulse experiment under no-growth conditions. Significant cell elution was observed and quantified for all conditions/systems. The results of these experiments allowed us to differentiate the effects associated with microbial lag and growth, two coupled processes whose impacts on the biodegradation and transport of contaminants can be difficult to distinguish.     

Virus transport in physically and geochemically heterogeneous subsurface porous media

A two-dimensional model for virus transport in physically and geochemically heterogeneous subsurface porous media is presented. The model involves solution of the advection-dispersion equation, which additionally considers virus inactivation in the solution, as well as virus removal at the solid matrix surface due to attachment (deposition), release, and inactivation. Two surface inactivation models for the fate of attached inactive viruses and their subsequent role on virus attachment and release were considered. Geochemical heterogeneity, portrayed as patches of positively charged metal oxyhydroxide coatings on collector grain surfaces, and physical heterogeneity, portrayed as spatial variability of hydraulic conductivity, were incorporated in the model. Both layered and randomly (log-normally) distributed physical and geochemical heterogeneities were considered. The upstream weighted multiple cell balance method was employed to numerically solve the governing equations of groundwater flow and virus transport. Model predictions show that the presence of subsurface layered geochemical and physical heterogeneity results in preferential flow paths and thus significantly affect virus mobility. Random distributions of physical and geochemical heterogeneity have also notable influence on the virus transport behavior. While the solution inactivation rate was found to significantly influence the virus transport behavior, surface inactivation under realistic field conditions has probably a negligible influence on the overall virus transport. It was further demonstrated that large virus release rates result in extended periods of virus breakthrough over significant distances downstream from the injection sites. This behavior suggests that simpler models that account for virus adsorption through a retardation factor may yield a misleading assessment of virus transport in "hydrogeologically sensitive" subsurface environments.     

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.     

Biodegradation during contaminant transport in porous media: 1. mathematical analysis of controlling factors

Interest in coupled biodegradation and transport of organic contaminants has expanded greatly in the past several years. In a system in which biodegradation is coupled with solute transport, the magnitude and rate of biodegradation is influenced not only by properties of the microbial population and the substrate, but also by hydrodynamic properties (e.g., residence time, dispersivity). By nondimensionalizing the coupled-process equations for transport and nonlinear biodegradation, we show that transport behavior is controlled by three characteristic parameters: the effective maximum specific growth rate, the relative half-saturation constant, and the relative substrate-utilization coefficient. The impact on biodegradation and transport of these parameters, which constitute various combinations of factors reflecting the influences of biotic and hydraulic properties of the system, are examined numerically. A type-curve diagram based on the three characteristic parameters is constructed to illustrate the conditions under which steady and non-steady transport is observed, and the conditions for which the linear, first-order approximation is valid for representing biodegradation. The influence of constraints to microbial growth and substrate utilization on contaminant transport is also briefly discussed. Additionally, the impact of biodegradation, with and without biomass growth, on spatial solute distribution and moments is examined.     

Stability of titania nanoparticles in soil suspensions and transport in saturated homogeneous soil columns

The stability of TiO₂ nanoparticles in soil suspensions and their transport behavior through saturated homogeneous soil columns were studied. The results showed that TiO₂ could remain suspended in soil suspensions even after settling for 10 days. The suspended TiO₂ contents in soil suspensions after 24 h were positively correlated with the dissolved organic carbon and clay content of the soils, but were negatively correlated with ionic strength, pH and zeta potential. In soils containing soil particles of relatively large diameters and lower solution ionic strengths, a significant portion of the TiO₂ (18.8-83.0%) readily passed through the soils columns, while TiO₂ was significantly retained by soils with higher clay contents and salinity. TiO₂ aggregate sizes in the column outflow significantly increased after passing through the soil columns. The estimated transport distances of TiO₂ in some soils ranged from 41.3 to 370 cm, indicating potential environmental risk of TiO₂ nanoparticles to deep soil layers.     

The influence of substrate and electron acceptor availability on bioactive zone dynamics in porous media

Two approaches were used to investigate the influence of dissolved oxygen (DO) and substrate availability on the formation and dynamics of "bioactive zones" in a water-saturated porous medium. A bioactive zone is defined as a region where a microbial community is sufficiently active to metabolize bioavailable substrates. In the first approach, microbial activity was characterized by monitoring the spatial and temporal variability of DO and aqueous substrate (salicylate and naphthalene) concentrations during miscible-displacement experiments. In the second approach, microbial activity was monitored using multiple fiber optics emplaced in the porous medium to detect luminescence produced by Pseudomonas putida RB1353, a bioluminescent reporter organism that produces light when salicylate (an intermediate of naphthalene degradation) is present. The results of both approaches show that the location and size of the bioactive zones were influenced by in situ DO and substrate availability. When DO was not a limiting factor (i.e., lower substrate input concentrations), the bioactive zone encompassed the entire column, with the majority of the microbial activity occurring between the inlet and midpoint. However, as the availability of DO became limiting for the higher substrate input experiments, the size of the bioactive zone shrank and was ultimately limited to the proximity of the column inlet.     

The effect of a biofilm on solute diffusion in fractured porous media

At sites in fractured rock where contamination has been exposed to the rock matrix for extended periods of time, the amount of contaminant mass residing in the matrix can be considerable. Even though it may be possible to diminish concentrations by the advection of clean water through the fracture features, back diffusion from mass held in the matrix will lead to a continuing source of contamination. In such an event, the development of a biofilm (a thin film of microbial mass) on the wall of the fractures may act to limit or prevent the back diffusion process. The objective of this preliminary study is to explore the influence imparted by the presence of a biofilm on the process of matrix diffusion. The investigation was conducted using radial diffusion cells constructed from rock core in which biofilm growth was stimulated in a central reservoir. Once biofilms were developed, forward diffusion experiments were conducted in which a conservative solute migrated from the central reservoir into the intact rock sample. Diffusion experiments were performed in a total of 11 diffusion cell pairs where biofilm growth was stimulated in one member of the pair and inhibited in the other. The effect of the presence of a biofilm on tracer diffusion was determined by comparison of the diffusion curves produced by each cell pair. A semi-analytical model that accounts for the presence of a biofilm was used to investigate the effect of the biofilm on mass transfer due to changes in the effective porosity, effective diffusion coefficient, and the depth of penetration of the biofilm into the intact rock. The results show that the biofilm acted to plug the rock matrix, rather than forming a discrete layer on the reservoir surface. The reduction in effective porosity due to the biofilm ranged from 6% to 52% with the majority of the samples in the 30% to 50% range. Based on the present results, with more efficient biofilm stimulation, it is reasonable to assume that a more complete plugging of the microcrack porosity might be possible, leaving a much thicker and efficient barrier than could be achieved via a surface biofilm.     

Transport of a decay chain in homogenous porous media: analytical solutions

With the aid of integral transforms, analytical solutions for the transport of a decay chain in homogenous porous media are derived. Unidirectional steady-state flow and radial steady-state flow in single and multiple porosity media are considered. At least in Laplace domain, all solutions can be written in closed analytical formulae. Partly, the solutions can also be inverted analytically. If not, analytical calculation of the steady-state concentration distributions, evaluation of temporal moments and numerical inversion are still possible. Formulae for several simple boundary conditions are given and visualized in this paper. The derived novel solutions are widely applicable and are very useful for the validation of numerical transport codes.     

Effects of pH and ionic strength on sulfamethoxazole and ciprofloxacin transport in saturated porous media

Many antibiotics regarded as emerging contaminants have been frequently detected in soils and groundwater; however, their transport behaviors in soils remain largely unknown. This study examined the transport of two antibiotics, sulfamethoxazole (SMZ) and ciprofloxacin (CIP), in saturated porous media. Laboratory columns packed with quartz sand was used to test the effects of solution pH and ionic strength (IS) on their retention and transport. The results showed that these two antibiotics behaved differently in the saturated sand columns. In general, SMZ manifested a much higher mobility than CIP for all experimental conditions tested. Almost all SMZ transported through the columns within one pore volume in deionized water (i.e., pH=5.6, IS=0), but no CIP was detected in the effluents under the same condition after extended column flushing. Perturbations in solution pH (5.6 and 9.5) and IS (0 and 0.1M) showed no effect on SMZ transport in the saturated columns. When pH increased to 9.5, however, ~93% of CIP was eluted from the sand columns. Increase of IS from 0 to 0.1M also slightly changed the distribution of adsorbed CIP within the sand column at pH 5.6, but still no CIP was detected in the effluents. A mathematical model based on advection-dispersion equation coupled with equilibrium and kinetic reactions successfully simulated the transport of the antibiotics in water-saturated porous media with R(2)=0.99.     

Effect of fullerol nanoparticles on the transport and release of copper ions in saturated porous media

Environmental Science and Pollution Research - While the application and discharge of carbon nanomaterials (CNMs) increased rapidly, the research on the environmental safety of CNMs is also...     

Influence of permeability on nanoscale zero-valent iron particle transport in saturated homogeneous and heterogeneous porous media

Environmental Science and Pollution Research - Nanoscale zero-valent iron (NZVI) particles can be used for in situ groundwater remediation. The spatial particle distribution plays a very important...     

Illuminating reactive microbial transport in saturated porous media: demonstration of a visualization method and conceptual transport model

We demonstrate a method to study reactive microbial transport in saturated translucent porous media using the bacteria Pseudomonas fluorescens 5RL genetically engineered to carry a plasmid with bioluminescence genes inducible by salicylate. Induced bacteria were injected into a cryolite grain filled chamber saturated with a sterile non-growth-promoting (phosphorus limited) chemical mixture containing salicylate as an aromatic hydrocarbon analogue. The amount of light produced by the bacteria serves as an estimator of the relative efficiency of aerobic biodegradation since bioluminescence is dependent on both salicylate and oxygen but only consumes oxygen. Bioluminescence was captured with a digital camera and analyzed to study the evolving spatial pattern of the bulk oxygen consuming reactions. As fluid flow transported the bacteria through the chamber, bioluminescence was observed to initially increase until an oxygen depletion zone developed behind the advective front. Bacterial transport was modeled with the advection dispersion equation and oxygen concentration was modeled assuming bacterial consumption via Monod kinetics with consideration of additional effects of rate-limited mass transfer from residual gas bubbles. Consistent with previous measurements, bioluminescence was considered proportional to oxygen consumed. Using the observed bioluminescence, model parameters were fit that were consistent with literature values and produced results in good agreement with the experimental data. These findings demonstrate potential for using this method to investigate the complex spatial and temporal dynamics of reactive microbial transport in saturated porous media.     

The effect of surface-active solutes on water flow and contaminant transport in variably saturated porous media with capillary fringe effects

Organic contaminants that decrease the surface tension of water (surfactants) can have an effect on unsaturated flow through porous media due to the dependence of capillary pressure on surface tension. We used an intermediate-scale 2D flow cell (2.44 x 1.53 x 0.108 m) packed with a fine silica sand to investigate surfactant-induced flow perturbations. Surfactant solution (7% 1-butanol and dye tracer) was applied at a constant rate at a point source located on the soil surface above an unconfined synthetic aquifer with ambient groundwater flow and a capillary fringe of approximately 55 cm. A glass plate allowed for visual flow and transport observations. Thirty instrumentation stations consist of time domain reflectometry probes and tensiometers measured in-situ moisture content and pressure head, respectively. As surfactant solution was applied at the point source, a transient flow perturbation associated with the advance of the surfactant solution was observed. Above the top of the capillary fringe the advance of the surfactant solution caused a visible drainage front that radiated from the point source. Upon reaching the capillary fringe, the drainage front caused a localized depression of the capillary fringe below the point source because the air-entry pressure decreased in proportion to the decrease in surface tension caused by the surfactant. Eventually, a new capillary fringe height was established. The height of the depressed capillary fringe was proportional to height of the initial capillary fringe multiplied by the relative surface tension of the surfactant solution. The horizontal transport of surfactant in the depressed capillary fringe, driven primarily by the ambient groundwater flow, caused the propagation of a wedge-shaped drying front in the downgradient direction. Comparison of dye transport during the surfactant experiment to dye transport in an experiment without surfactant indicated that because surfactant-induced drainage decreased the storage capacity of the vadose zone, the dye breakthrough time to the water table was more than twice as fast when the contaminant solution contained surfactant. The extensive propagation of the drying front and the effect of vadose zone drainage on contaminant breakthrough time suggest the importance of considering surface tension effects on unsaturated flow and transport in systems containing surface-active organic contaminants or systems, where surfactants are used for remediation of the vadose zone or unconfined aquifers.     

Transport of volatile compounds in porous media in the presence of a trapped gas phase

The presence of an immobile gaseous phase in an otherwise-saturated porous medium affects the transport of volatile compounds. The linear theory of partitioning tracers suggests that a volatile tracer introduced into such a system should be retarded with a constant retardation factor. Using high concentrations, however, the saturation of the gaseous phase will change as an effect of the tracer test itself. Competitive gas transfer among all volatile compounds and the change of saturation may lead to tracer concentrations that are temporarily higher than those injected. We analyze the system in the framework of the coherence theory by Helfferich [Soc. Pet. Eng. J. 21 (1) (1981) 51]. The governing equations are formulated as functions of total concentration, i.e., the mass of solutes in all phases per pore volume. Neglecting dispersion and mass-transfer kinetics, we derive the characteristic form of the resulting system of hyperbolic equations. In a system with N volatile compounds, a variation of the concentrations splits up into N waves, each traveling with its own characteristic velocity. If the presence of a gaseous phase is sustained, one wave will be a standing one. We perform numerical model calculations for tracers with various Henry's law coefficients and show that the results agree with the semi-analytical solution obtained by coherence theory.     

Migration of saline solutions in variably saturated porous media

Migration of concentrated NaNO3 solutions in homogeneous packs of pre-wetted silica sands was investigated using a light transmission system. Solutions of 5 molal NaNO3 were found to migrate downward 24-62% faster than pure water, in an unstable, fingered manner. This behavior was attributed primarily to a surface tension induced, non-zero apparent contact angle between the imbibing and the resident fluids. For saline solutions of similar surface tension to that of pure water (achieved by the addition of 2% methanol), the migration rates and plume shapes were comparable to that of water, demonstrating that density was not the primary source of the observed differences in migration patterns. At depths where resident saturation increased above residual, the migration process appeared to occur via film flow with slight changes in saturation (<4%), rather than in a series of abrupt jumps, as observed at shallower depths. A method for contact angle scaling was used to illustrate the effects of non-zero contact angles on capillary pressure-saturation curves.     

The influence of field-scale heterogeneity on the infiltration and entrapment of dense nonaqueous phase liquids in saturated formations

Numerical simulations are used for the systematic exploration of the migration and entrapment of dense nonaqueous phase liquids (DNAPLs) in heterogeneous formations. Ensembles of realizations of random, spatially correlated permeability fields are generated and employed in model simulations of a spill event. Statistical techniques are then used to quantify the sensitivity of model predictions to input parameters, thereby identifying the parameters or processes that may be of primary importance in the determination of organic liquid distributions in heterogeneous systems. Results of the study indicate that the most critical factors in modeling organic entrapment include the spill release rate, reliable estimates of the mean, variance, and vertical correlation scale of the formation permeability, and an accurate representation of the correlation between the capillary pressure–saturation function and the permeability. In contrast, the hydraulic gradient and cross-correlation of residual saturations with permeabilities are found to have only minor influence on organic liquid distributions in such heterogeneous formations.     

Effect of goethite coating and humic acid on the transport of bacteriophage PRD1 in columns of saturated sand

The transport of bacteriophage PRD1, a model virus, was studied in columns containing sediment mixtures of quartz sand with goethite-coated sand and using various solutions consisting of monovalent and divalent salts and humic acid (HA). Without HA and in the absence of sand, the inactivation rate of PRD1 was found to be as low as 0.014 day(-1) (at 5+/-3 degrees C), but in the presence of HA it was much lower (0.0009 day(-1)), indicating that HA helps PRD1 to survive. When the fraction of goethite in the sediment was increased, the removal of PRD1 also increased. However, in the presence of HA, C/C0 values of PRD1 increased by as much as 5 log units, thereby almost completely eliminating the effect of addition of goethite. The sticking efficiency was not linearly dependent on the amount of goethite added to the quartz sand; this is apparently due to surface charge heterogeneity of PRD1. Our results imply that, in the presence of dissolved organic matter (DOM), viruses can be transported for long distances thanks to two effects: attachment is poor because DOM has occupied favourable sites for attachment and inactivation of virus may have decreased. This conclusion justifies making conservative assumptions about the attachment of viruses when calculating protection zones for groundwater wells.