Recent studies indicate that during in situ bioremediation of contaminated groundwater, degradation occurs primarily along transverse mixing zones. Classical reactive-transport models overpredict the amount of degradation because solute spreading and mixing are not distinguished. Efforts to correct this have focused on modifying both dispersion and reaction terms, but no consensus on the best approach has emerged. In this work, a pore-scale model was used to simulate degradation along a transverse mixing zone between two required nutrients, and a continuum model with fitted parameters was used to match degradation rates from the pore-scale model. The pore-scale model solves for the flow field, concentration field, and biomass development within pore spaces of porous medium. For the continuum model, the flow field and biomass distributions are assumed to be homogeneous, and the fitting parameters are the transverse dispersion coefficient (DT) and maximum substrate utilization rate (kS,c). Results from the pore-scale model show that degradation rates near the system inlet are limited by the reaction rate, while degradation rates downgradient are limited by transverse mixing. For the continuum model, the value of DT may be adjusted so that the degradation rate with distance matches that from the pore-scale model in the mixing-limited region. However, adjusting the value of kS only improves the fit to pore-scale results within the reaction-limited region. Comparison with field and laboratory experiments suggests that the length of the reaction rate-limited region is small compared to the length scale over which degradation occurs. This indicates that along transverse mixing zones in the field, values of kS are unimportant and only the value of DT must be accurately fit.
G. Gopalakrishnan, Negri, C. M., Minsker, B. S., and Werth, C. J., “
This paper proposes a method of assessing the distribution of chlorinated solvents in soil and ground water using tree branches. Sampling branches is a potentially more cost‐effective and easier method than sampling tree cores, with less risk of damage to the tree. This approach was tested at Argonne National Laboratory, where phytoremediation is being used to remove tetrachloroethene (PCE), trichloroethene (TCE), and carbon tetrachloride (CCl4) from soil and ground water. The phytoremediation system consists of shallow‐rooted willows planted in an area with contaminated soil and deep‐rooted poplars planted in an area with clean soil and contaminated ground water. Branch samples were collected from 126 willows and 120 poplars. Contaminant concentrations from 31 soil borings and six monitoring wells were compared to those from branches of adjacent trees. Regression equations with correlation coefficients of at least 0.89 were obtained, which were found to be chemical specific. Kriged profiles of TCE concentration based on soil and willow branch data were developed and showed good agreement. Profiles based on ground water data could not be developed due to lack of sufficient monitoring wells for a meaningful statistical analysis. An analytical model was used to simulate TCE concentrations in tree branches from soil concentrations; the diffusion coefficient for TCE in the tree was used as the fitting parameter and the best‐fit value was two orders of magnitude greater than literature values. This work indicates that tree branch sampling is a useful approach to assess contaminant distribution and potentially to determine where to locate monitoring wells or perform detailed soil analysis. Further research is necessary prior to using this method as a quantitative monitoring tool for soil and ground water.
Several studies have demonstrated that the success of natural and engineered in situ remediation of groundwater pollutants relies on the transverse mixing of reactive chemicals or nutrients along plume margins. Efforts to predict reactions in groundwater generally rely on dispersion coefficients obtained from nonreactive tracer experiments to determine the amount of mixing, but these coefficients may be affected by spreading, which does not contribute to reaction. Mixing is controlled only by molecular diffusion in pore spaces, and the length scale of transverse mixing zones can be small, often on the order of millimeters to centimeters. We use 2D pore‐scale simulation to investigate whether classical transverse dispersion coefficients can be applied to model mixing‐controlled reactive transport in three different porous media geometries: periodic, random, and macroscopically trending. The lattice‐Boltzmann method is used to solve the steady flow field; a finite volume code is used to solve for reactive transport. Nonreactive dispersion coefficients are determined from the transverse spreading of a conservative tracer. Reactive dispersion coefficients are determined by fitting a continuum model which calculates the total product formation as a function of distance to the results from our pore scale simulation. Nonreactive and reactive dispersion coefficients from these simulations are compared. Results indicate that, regardless of the geometrical properties of the media, product formation can be predicted using transverse dispersion coefficients determined from a conservative tracer, provided dispersion coefficients are determined beyond some critical distance downgradient where the plume has spread over a sufficiently large transverse distance compared to the mean grain diameter. This result contrasts with other studies where reactant mixing was controlled by longitudinal hydrodynamic dispersion; in those studies longitudinal dispersion coefficients determined from nonreactive tracer experiments over‐estimated the extent of reaction and product formation. Additional work is called for in order to confirm that these findings hold for a wider variety of grain sizes and geometries.
Pd-based catalysts provide efficient and selective reduction of several drinking water contaminants, but their long-term application requires effective treatments for catalyst regeneration following fouling by constituents in natural waters. This study tested alumina-supported Pd−Cu and Pd−In bimetallic catalysts for nitrate reduction with H2 after sulfide fouling and oxidative regeneration procedures. Both catalysts were severely deactivated after treatment with μM levels of sulfide. Regeneration was attempted with dissolved oxygen, hydrogen peroxide, sodium hypochlorite, and heated air. Only sodium hypochlorite and heated air were effective regenerants, specifically restoring nitrate reduction rates for a Pd−In/γ-Al2O3 catalyst from 20% to between 39 and 60% of original levels. Results from ICP−MS revealed that sodium hypochlorite caused dissolution of Cu from the Pd−Cu catalyst but that the Pd−In catalyst was chemically stable over a range of sulfide fouling and oxidative regenerative conditions. Analysis by XPS indicated that PdS and In2S3 complexes form during sulfide fouling, where sulfur is present as S2-, and that regeneration with sodium hypochlorite converts a portion of the S2- to S6+, with a corresponding increase in reduction rates. These results indicate that Pd−In catalysts show exceptional promise for being robust under fouling and regeneration conditions that may occur when treating natural waters.
The ability of chitin fermentation products to promote tetrachloroethene (PCE) reduction was evaluated in a continuous-flow column system to identify how different electron donors affect reductive dechlorination. Natural chitin fermentation products were initially used to support PCE reduction. Acetate (3.5mM) was the dominant fermentation product, followed by propionate (0.1mM), butyrate (0.1mM), and hydrogen (100nM). After chlorinated ethene concentration profiles reached pseudo steady state, the ability of individual fermentation products (acetate, acetate+propionate, propionate, or formate) to support PCE reduction was evaluated. None of the fermentation products tested stimulated dechlorination as well as the suite generated from chitin (kPCE=6.9day−1); however, acetate-stimulated PCE dechlorination the best (kPCE=5.3day−1), followed by formate (kPCE=2.4day−1), acetate+propionate (kPCE=1.8day−1), and propionate (kPCE=1.2day−1). Similar trends were observed for the PCE daughter products trichloroethene and dichloroethene. Free energies of individual fatty acid reactions were calculated and shown to be useful predictors of dechlorination performance, except for the case of acetate+propionate. Hence, acetate is the dominant fatty acid controlling dechlorination in the chitin-enhanced system, propionate appears to have an inhibitory effect when present with acetate alone, and other unidentified nutrients produced during chitin fermentation likely contribute to dechlorination activity as well.
Chitin, corncobs, and a mixture of chitin and corncobs were tested as potential electron donor sources for stimulating the reductive dechlorination of tetrachloroethene (PCE). Semi-batch, sand-packed columns were used to evaluate the donors with aerobic and anaerobic groundwaters containing varying degrees of alkalinity. In all experiments, acetate and butyrate were the dominant fatty acids produced, although propionate, valerate, formate, and succinate were also detected. From a multivariable regression analysis on the data, the presence of chitin, limestone, and dechlorinating culture inoculum were determined to be the most positive predictors of dechlorination activity. Chitin fermentation products supported the degradation of PCE to trichloroethene (TCE), cis-1,2-dichloroethene (DCE), and vinyl chloride (VC), even in columns containing PCE DNAPL, whereas dechlorination activity was not observed in any of the columns containing corncobs alone. The longevity and efficiency of chitin as an electron donor source demonstrates its potential usefulness for passive, in situ field applications.
Catalytic nitrate reduction was evaluated for the purpose of drinking water treatment. Common anions present in natural waters and humic acid were evaluated for their effects on NO3- hydrogenation over a bimetallic supported catalyst (Pd−Cu/γ-Al2O3). Groundwater samples, with and without powder activated carbon (PAC) pretreatment, were also evaluated. In the absence of inhibitors the NO3- reduction rate was 2.4 × 10-01 L/min g cat. However, the addition of constituents (SO42-, SO32-, HS-, Cl-, HCO3-, OH-, and humic acid) on the order of representative concentrations for drinking water decreased the NO3- reduction rate. Sulfite, sulfide, and elevated chloride decreased the NO3- reduction rate by over 2 orders of magnitude. Preferential adsorption of Cl- inhibited NO3- reduction to a greater extent than NO2- reduction. Partial regeneration of catalysts exposed to SO32- was achieved by using a dilute hypochlorite solution, however Cu dissolution occurred. Dissolved constituents in the groundwater sample decreased the NO3- reduction rate to 3.7 × 10-03 L/min g cat and increased ammonia production. Removal of dissolved organic matter from the groundwater using PAC increased the NO3- reduction rate to 5.06 × 10-02 L/min g cat and decreased ammonia production. Elemental analyses of catalysts exposed to the natural groundwater suggest that mineral precipitation may also contribute to catalyst fouling.
Transverse dispersion across adjacent streamlines can control the amount of mixing and reaction between one or more contaminants and a limiting substrate along the fringes of groundwater plumes. Streamlines in groundwater converge and diverge in heterogeneous porous media, depending on the permeability distribution. When flow is focused in a high‐permeability zone, the distance required for a solute to cross a given number of streamlines decreases, and the time allowed for mixing and reaction is reduced. Because the first effect outweighs the latter, the overall result is an enhancement of transverse mixing and reaction. Here we develop a conceptual model of heterogeneous two‐dimensional structures facilitating flow focusing. We use the conceptual model to develop simple analytical expressions quantifying the extent to which mixing and reaction are enhanced when flow focusing occurs and compare these to results of numerical simulations. Significant enhancement of transverse mixing and reaction by flow focusing is observed; for the cases considered, flow focusing enhances the amount of reaction by a factor ranging from 1.8 to 11.9. The relatively simple analytical expressions demonstrate that the fraction of the domain height made up by high‐permeability inclusions, the fraction of flow that passes through the inclusions, and the fringe bypassing of inclusions determine the amount of mixing and reaction enhancement for the permeability distributions considered. These results partially explain why field‐scale dispersivities are larger than laboratory derived dispersivities, where homogeneous and isotropic sediments are typically used. Further work is needed to verify the theoretical results presented here with laboratory and field experiments and to expand the relatively simple analytical expressions to consider more heterogeneous three‐dimensional permeability fields.
To better understand sorption, separation methods are needed to enrich soils and sediments in one or more types of carbonaceous materials (CM), especially in fine grain materials where physical separation is not possible. We evaluated a series of chemical and thermal treatment methods by applying them to four different CMs prepared in our laboratory: a humic acid (HA), a char, a soot, and a heat-treated soot (HN-soot). Before and after each treatment step, CM properties were evaluated including aqueous phase sorption with trichloroethene (TCE). Results indicate that treatment with hydrofluoric (HF) and hydrochloric acid (HCl) to remove silicate minerals, and with trifluoroacetic acid (TFA) to remove easily hydrolyzable organic matter, has relatively little effect on the humic acid mass (<19% change) and TCE sorption to this material. Subsequent treatment with NaOH to extract fulvic and humic acids results in almost complete removal of the humic acid mass (>92%) and has little to no effect on the masses of the char and two soots (<8% change) and TCE sorption to these materials. Treatment with acid dichromate to remove kerogen and humin also has little effect on masses of the char and soots (<16% change), but TCE sorption to these materials is significantly altered (by >10× in some cases), and there is strong evidence of surface oxidation based on X-ray photoelectron and diffuse reflectance Fourier transform infrared spectroscopy results. The last step, thermal treatment, which targets char removal, also destroys >96% of the soots pretreated with acid dichromate. However, when thermal treatment is applied to the original soots, <32% of these materials are destroyed. Thermal oxidation also affects sorption to one of the soots (by ~2× at low concentration), and surface oxidation is evident. These results suggest that treatment with HCl, HCl/HF, TFA, and NaOH can be applied to soils and sediments to obtain CM enrichment fractions for sorption evaluation, but that acid dichromate and heat treatment may not be appropriate for these purposes.
The success of in situ bioremediation projects depends on the mixing of contaminants and nutrients in the presence of microbes. In this work, a pore-scale model is developed to simulate biomass growth that is controlled by the mixing of an electron donor and acceptor. A homogeneous packing of cylinders representing solid grains is used as the model two-dimensional porous medium. The system is initially seeded with microbes in computational cells located at grain-water interfaces. The solutes enter the system completely unmixed; each solute is input over one half of the inlet boundary. Solute mixing is controlled by molecular diffusion transverse to the flow direction, and solutes are biotransformed according to dual Monod kinetics only where biomass is present. Simulation of biomass growth requires calculation of the water flow field as well as transport and reaction of solutes. The lattice Boltzmann method is used to obtain the flow field. Transport and reaction of the solutes is modeled by a finite volume discretization of the advection-diffusion-reaction equation. Biomass is allowed to grow and spread by means of a cellular automata algorithm. Model parameters are systematically varied to understand their effects on biomass development. Base case parameter values are obtained from batch experiments reported in the literature and are modified to achieve agreement between simulation results and previously reported micromodel experimental results. The most significant mechanisms that control biomass development are shear strength of new biomass and solute degradation rates. The biomass growth model achieves good qualitative agreement with experimental results.
The effects of heterogeneous grain packing on colloid transport were evaluated in flow-through columns using magnetic resonance imaging (MRI). Two columns were packed, each with a core of fine-grained silica gel surrounded by a shell of coarse-grained silica gel. In column 1, 600–850 μm silica gel was surrounded by 850–1000 μm silica gel. In column 2, 250–600 μm silica gel was surrounded by 850–1000 μm silica gel. Both columns were continuously purged with water and colloids were introduced as pulses.MRI images of column 1 showed that colloid transport in the core and shell was not distinguishable. However, colloid transport was slightly faster along the bottom of the column. T1-weighted images showed that small variations in the packing density of silica gel caused this effect. MRI images of column 2 showed that colloid transport in the core was much slower than colloid transport in the shell. Colloid exchange between the shell and the core was also observed.Colloid transport velocities and collision efficiencies were calculated from the images. In agreement with the visualization, velocities for column 1 increased from the top to bottom of the column and velocities for column 2 were greater in the shell than in the core. Collision efficiencies were calculated, but trends were not apparent because of the difficulty of applying filtration theory to heterogeneous media. Velocities from images were compared to those from conventional experiments where colloid concentrations were measured at the column effluent. While often comparable, results from the latter mask many of the complexities that control the overall rate of colloid transport. Since these complexities can give rise to very different transport behavior, it is critical to understand their effects in real systems. Hence, MRI is a technique that has the power to elucidate many of the small-scale processes that affect the behavior of colloids in the field.
A field-scale compacted soil liner was constructed at the University of Illinois at Urbana-Champaign by the U.S. Environmental Protection Agency (USEPA) and Illinois State Geological Survey in 1988 to investigate chemical transport rates through low permeability compacted clay liners (CCLs). Four tracers (bromide and three benzoic acid tracers) were each added to one of four large ring infiltrometers (LRIs) while tritium was added to the pond water (excluding the infiltrometers). Results from the long-term transport of Br− from the localized source zone of LRI are presented in this paper. Core samples were taken radially outward from the center of the Br− LRI and concentration depth profiles were obtained. Transport properties were evaluated using an axially symmetric transport model. Results indicate that (1) transport was diffusion controlled; (2) transport due to advection was negligible and well within the regulatory limits of ksat⩽1×10−7cm/s; (3) diffusion rates in the horizontal and vertical directions were the same; and (4) small positioning errors due to compression during soil sampling did not affect the best fit advection and diffusion values. The best-fit diffusion coefficient for bromide was equal to the molecular diffusion coefficient multiplied by a tortuosity factor of 0.27, which is within 8% of the tortuosity factor (0.25) found in a related study where tritium transport through the same liner was evaluated. This suggests that the governing mechanisms for the transport of tritium and bromide through the CCL were similar. These results are significant because they address transport through a composite liner from a localized source zone which occurs when defects or punctures in the geomembrane of a composite system are present.
Desorption profiles of trichloroethylene (TCE), tetrachloro- ethylene (PCE), and a TCE−PCE mixture were measured for three natural solids and four zeolites. Initial sorbed mass (Mi) in slow desorbing sites of natural solids and in micropores of zeolites were obtained from desorption profiles. In natural solids, Mi increases with recalcitrant organic matter content. In zeolites, Mi generally increases with decreasing micropore width and increasing micropore hydrophobicity, but the effect of hydrophobicity is stronger. In both natural solids and zeolites, competition between TCE and PCE causes Mi for each sorbate in the mixture to be less than or similar to that for each sorbate alone. Zeolite results indicate that micropore width affects this competition more than micropore hydrophobicity for the solids examined. Desorption in all solids was simulated with the radial diffusion model, either alone or coupled with the advection−dispersion equation when necessary; diffusion rate constants (D/R2) were obtained. In natural solids, mean values of D/R2 increase with decreasing recalcitrant organic matter content. In zeolites, values of D/R2 generally increase with increasing micropore width, while they are a weak function of hydrophobicity. In both natural solids and zeolites, competition between TCE and PCE causes D/R2 for each sorbate in the mixture to generally be larger than that for each sorbate alone. Zeolite results indicate that the effects of competition on D/R2 generally decrease with decreasing micropore width for the solids examined; a trend with micropore hydrophobicity is not apparent. For the three natural solids and four zeolites examined in this study, the similar effects of competition between TCE and PCE on values of Mi and D/R2 and the overlapping range of D/R2 values support the hypothesis that diffusion through hydrophobic micropores affects and may control slow mass transfer processes in the recalcitrant organic matter of natural solids. These results contribute to the fundamental understanding of slow mass transfer processes in natural solids, and they indicate that characterization of micropore width and polarity may be necessary to predict organic chemical transport and fate.
A new experimental approach and complementary model analysis are presented for studying colloid transport and fate in porous media. The experimental approach combines high precision etching to create a controlled pore network in a silicon wafer (i.e., micromodel), with epifluorescent microscopy. Two different sizes of latex colloids were used; each was stained with a fluorescent dye. During an experiment, water with colloids was purged through a micromodel at different flow rates. Flow paths and particle velocities were determined and compared with flow paths calculated using a two-dimensional (2D) lattice Boltzmann (LB) model. For 50% of the colloids evaluated, agreement between measured and calculated flow paths and velocities were excellent. For 20%, flow paths agreed, but calculated velocities were less. This is attributed to the parabolic velocity profile across the micromodel depth, which was not accounted for in the 2D flow model. For 12%, flow paths also agreed, but calculated velocities were less. These colloids were close to grain surfaces, where model errors increase. Also, particle–surface interactions were not accounted for in the model; this may have contributed to the discrepancy. For the remaining 18% of colloids evaluated, neither flow paths nor velocities agreed. The majority of colloids in this last case were observed after breakthrough, when concentrations were high. The discrepancies may be due to particle–particle interactions that were not accounted for in the model. Filtration efficiencies for all colloid sizes at different flow rates were calculated from filtration theory. Attachment rates were obtained from successive images during an experiment. With these, attachment efficiencies were calculated, and these agreed with literature values. The study demonstrates that excellent agreement between experimental and model results for colloid transport at the pore scale can be obtained. The results also demonstrate that when experimental and model results do not agree, mechanistic inferences and system limitations can be evaluated.
A series of interactive web simulation models were developed to help students understand the coupled physical, chemical, and microbiological processes that affect the transport and fate of pollutants in groundwater. Conventional models that simulate coupled processes are often not effective learning tools because they are too complex, they suffer from cumbersome interfaces, and/or they are difficult to install and run. The web models are fully interactive Java applets that run locally through a web browser. They have graphical user interfaces, straightforward input and output fields, and rapid response times. These features enhance learning because students can rapidly visualize the impact of changes to parameter values and boundary and initial conditions, and explore the effect of different reaction processes. Presently, six different web models have been developed to explore coupled processes such as advection, longitudinal and transverse dispersion, linear or rate limited sorption, and first order decay. A web model was also developed to study the flow patterns caused by multiple pumping wells in two‐dimensional steady flow. Several examples of how the models can be used to teach students about coupled processes are discussed. Last, an assessment of the effectiveness of the models to enhance student learning is presented.
Predicting the dissolution rate of nonaqueous phase liquids (NAPLs) in groundwater is difficult, as the effects of variable pore and NAPL blob geometry are poorly understood. To elucidate these effects, fluorescence microscopy and digital image analysis were used to quantify the size and location of variably distributed NAPL blobs during dissolution in homogeneous and heterogeneous pore networks etched into silicon wafers. Results show that the dissolution rate constant (expressed as the Sherwood number, Sh) is relatively constant regardless of pore and NAPL blob geometry when the average mass transfer length scale remains constant during dissolution. Results also show that Sh increases with Peclet (Pe) between 2 and 26 and then levels off. The limiting value of Sh reached depends on the average diffusion length scale; this length scale was directly calculated and found to vary depending on the pore and NAPL blob geometry. For example, the average diffusion length scale decreases (and Sh increases) as the pore throat width to grain diameter increases. Last, results show that the volumetric NAPL content (θn) is linearly related to the specific NAPL-water interfacial area (ait) over much of the dissolution process. However, this relationship depends on the pore and blob size distribution. For example, when multipore blobs control dissolution, the relationship between these parameters will change as smaller blobs dominate dissolution at low θn. These results are important because existing mass transfer correlations do not account for limiting values of Sh that can be obtained at high Pe for the effect of blob or pore geometry on the average diffusion length scale (and therefore on Sh) or for the effect of pore geometry and transient blob size distribution on the relationship between ait and θn.
The anaerobic halorespiring microorganism, Sulfurospirillum multivorans, was observed in the pore structure of an etched silicon wafer to determine how flow hydrodynamics and mass transfer limitations along a transverse mixing zone affect biomass growth. Tetrachloroethene (PCE, an electron acceptor, 0.2 mM) and lactate (an electron donor, 2 mM) were introduced as two separate and parallel streams that mixed along a reaction line in the pore structure. The first visible biomass occupied a single line of pores in the direction of flow, a few pore bodies from the micromodel centerline. This growth was initially present as small aggregates; over time, these grew and fused to form finger-like structures with one end attached to downgradient ends of the silicon posts and the other end extending into pore bodies in the direction of flow. Biomass did not grow in pore throats as expected, presumably because shear forces were not favorable. Over the next few weeks, the line of growth migrated upward into the PCE zone and extended over a width of up to five pore spaces. When the PCE concentration was increased to 0.5 mM, the microbial biomass increased and growth migrated down toward the lactate side of the micromodel. A new analytical model was developed and used to demonstrate that transverse hydrodynamic dispersion likely caused the biomass to move in the direction observed when the PCE concentration was changed. The model was unable, however, to explain why growth migrated upward when the PCE concentration was initially constant. We postulate that this occurred because PCE, not lactate, sorbed to biofilm components and that biomass on the lactate side of the micromodel was limited in PCE. A fluorescent tracer experiment showed that biomass growth changed the water flow paths, creating a higher velocity zone in the PCE half of the micromodel. These results contribute to our understanding of biofilm growth and will help in the development of new models to describe this complex process.