Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.     

Long‐Term Impacts on Groundwater and Reductive Dechlorination Following Bioremediation in a Highly Characterized Trichloroethene DNAPL Source Area

High‐resolution soil and groundwater monitoring was performed to assess the long‐term impacts of bioremediation using bioaugmentation with a dechlorinating microbial consortium (and sodium lactate as the electron donor) in a well‐characterized trichloroethene (TCE) dense nonaqueous phase liquid (DNAPL) source area. Monitoring was performed up to 3.7 years following active bioremediation using a high‐density monitoring network that included several discrete interval multi‐level sampling wells. Results showed that despite the absence of lactate, lactate fermentation transformation products, or hydrogen, biogeochemical conditions remained favorable for the reductive dechlorination of chlorinated ethenes. In locations where soil data showed that TCE DNAPL sources persisted, local contaminant rebound was observed in groundwater, whereas no rebound or continuous decreases in chlorinated ethenes were observed in locations where DNAPL sources were treated. While ethene levels measured 3.7 years after active treatment suggested relatively low (2 to 30%) dechlorination of the parent TCE and daughter products, carbon stable isotope analysis showed that the extent of complete dechlorination was much greater than indicated by ethene generation and that the estimated first‐order rate constant describing the complete dechlorination of TCE at 3.7 years following active bioremediation was approximately 3.6 y–1. Overall, results of this study suggest that biological processes may persist to treat TCE for years after cessation of active bioremediation, thereby serving as an important component of remedial treatment design and long‐term attenuation.     

Demonstration of Enhanced Bioremediation in a TCE Source Area at Launch Complex 34, Cape Canaveral Air Force Station

The ability of bioremediation to treat a source area containing trichloroethene (TCE) present as dense nonaqueous phase liquid (DNAPL) was assessed through a laboratory study and a pilot test at Launch Complex 34, Cape Canaveral Air Force Center. The results of microcosm testing indicate that the indigenous microbial community was capable of dechlorinating TCE to ethene if amended with electron donor; however, bioaugmentation with a dechlorinating culture (KB-1; SiREM, Guelph, Ontario, Canada) significantly increased the rate of ethene formation. In microcosms, the activity of the dechlorinating organisms in KB-1 was not inhibited at initial TCE concentrations as high as 2 mM. The initially high TCE concentration in ground water (1.2 mM or 155 mg/L) did not inhibit reductive dechlorination, and at the end of the study, the average concentration of ethene (2.4 mM or 67 mg/L) was in stoichiometric excess of this initial TCE concentration. The production of ethene in stoichiometric excess in comparison to the initial TCE concentration indicates that the bioremediation treatment enhanced the removal of TCE mass (either sorbed to soil or present as DNAPL). Detailed soil sampling indicated that the bioremediation treatment removed greater than 98.5% of the initial TCE mass. Confirmatory ground water samples collected 22 months after the bioremediation treatment indicated that chloroethene concentrations had continued to decline in the absence of further electron donor addition. The results of this study confirm that dechlorination to ethene can proceed at the high TCE concentrations often encountered in source areas and that bioremediation was capable of removing significant TCE mass from the test plot, suggesting that enhanced bioremediation is a potentially viable remediation technology for TCE source areas. Dehalococcoides abundance increased by 2 orders of magnitude following biostimulation and bioaugmentation.     

Bioaugmentation in a Well‐Characterized Fractured Rock DNAPL Source Area

A field demonstration was performed at Edwards Air Force Base to assess bioaugmentation for treatment of a well‐characterized tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL) source area in fractured rock. Groundwater recirculation was employed to deliver remedial amendments, including bacteria, to facilitate reductive dechlorination and enhance DNAPL dissolution. An active treatment period of 9 months was followed by a 10‐month posttreatment rebound evaluation. Dechlorination daughter products were observed in both the shallow and deep fracture zones following treatment. In the shallow fracture zone, the calculated DNAPL mass removed was approximately equal to the DNAPL mass estimated using partitioning tracer testing, and no rebound in chlorinated ethenes or ethene was observed during the posttreatment period. A maximum DNAPL dissolution enhancement factor of 5 was observed in the shallow fracture zone. In the deep fracture zone, only approximately 45% of the DNAPL mass—as estimated via partitioning tracer testing—was removed and rebound in the total molar chlorinated ethenes + ethene was observed. The difference in behavior between the shallow and deep fracture zones was attributed to DNAPL architecture and the fracture flow field.     

Numerical modeling analysis of hydrodynamic and microbial controls on DNAPL pool dissolution and detoxification: Dehalorespirers in co-culture

Dissolution of dense non-aqueous phase liquid (DNAPL) contaminants like tetrachloroethene (PCE) can be “bioenhanced” via biodegradation, which increases the concentration gradient at the DNAPL–water interface. Model simulations were used to evaluate the impact of ecological interactions between different dehalorespiring strains and hydrodynamics on the bioenhancement effect and the extent of PCE dechlorination. Simulations were performed using a two-dimensional coupled flow-transport model, with a DNAPL pool source and two microbial species, Dehalococcoides mccartyi 195 and Desulfuromonas michiganensis, which compete for electron acceptors (e.g., PCE), but not for their electron donors. Under biostimulation, low v_x conditions, D. michiganensis alone significantly enhanced dissolution by rapidly utilizing aqueous-phase PCE. In co-culture under these conditions, D. mccartyi 195 increased this bioenhancement modestly and greatly increased the extent of PCE transformation. Although D. michiganensis was the dominant population under low velocity conditions, D. mccartyi 195 dominated under high velocity conditions due to bioclogging effects.     

Flowpath Independent Monitoring of Reductive Dechlorination Potential in a Fractured Rock Aquifer

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2-¹⁴C] cis -DCE microcosm experiments. Microcosms were prepared with depth-specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of ¹⁴C-labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems.     

Bioremediation Management Reduces Mass Discharge at a Chlorinated DNAPL Site

Adaptive site management and aggressive bioremediation in the source zone of a complex chlorinated dense nonaqueous phase liquid (DNAPL) site reduced total chlorinated hydrocarbon mass discharge by nearly 80%. Successful anaerobic bioremediation of chlorinated hydrocarbons can be impaired by inadequate concentrations of electron donors, competing electron acceptors, specific inhibitors such as chloroform, and potentially by high contaminant concentrations associated with residual DNAPL. At the study site, the fractured bedrock aquifer was impacted by a mixture of chlorinated solvents and associated daughter products. Concentrations of 1,1,2,2‐tetrachloroethane (1,1,2,2‐TeCA), 1,1,2‐trichloroethane (1,1,2‐TCA), and 1,2‐dichloroethane (1,2‐DCA) were on the order of 100 to 1000 mg/L. Chloroform was present as a co‐contaminant and background sulfate concentrations were approximately 400 mg/L. Following propylene glycol injections, concentrations of organohalide‐respiring bacteria including Dehalococcoides and Dehalogenimonas spp. increased by two to three orders of magnitude across most of the source area. Statistical analysis indicated that reaching volatile fatty acid concentrations greater than 1000 mg/L and depleting sulfate to concentrations less than 50 mg/L were required to achieve a Dehalococcoides concentration greater than the 10⁴ cells/mL recommended for generally effective reductive dechlorination. In a limited area, chloroform concentrations greater than 5 mg/L inhibited growth of Dehalococcoides populations despite the availability of electron donor and otherwise appropriate geochemical conditions. After implementing a groundwater recirculation system targeting the inhibited area, chloroform concentrations decreased permitting significant increases in concentrations of Dehalococcoides and vinyl chloride reductase gene copies.     

Experimental Study of the Effects of DNAPL Distribution on Mass Rebound

The release of stored dissolved contaminants from low permeability zones contributes to plume persistence beyond the time when dense nonaqueous phase liquid (DNAPL) has completely dissolved. This is fundamental to successfully meeting acceptable low concentrations in groundwater that are driven by site‐specific cleanup goals. The study goals were to assess the role of DNAPL entrapment morphology on mass storage and plume longevity. As controlled field studies are not feasible, two‐dimensional (2D) test tanks were used to quantify the significance of mass loading processes from source dissolution and stored mass rebound. A simple two‐layer soil domain representing a high permeable formation sand overlying a zone of lower permeability sand was used in the tests. DNAPL mass depletion through dissolution was monitored via X‐ray photon attenuation, and effluent samples were used to monitor the plume. These data enabled analysis of the DNAPL distribution, the dissolved plume, and the dissolved phase distribution within the low permeability layer. Tests in an intermediate tank showed that mass storage contributes substantially to plume longevity. Detectable effluent concentrations persisted long after DNAPL depletion. The small tank results indicated that the DNAPL morphology influenced the flow field and caused distinctive transport mechanisms contributing to mass storage. Zones of high DNAPL saturation at the interface between the low and high permeability layers exhibited flow bypassing and diffusion dominated transport into the low permeability layer. In the absence of a highly saturated DNAPL zone near the soil interface the contaminant penetrated deeper into the low permeability layer caused by a combination of advection and diffusion.     

Evaluation of an upscaled model for DNAPL dissolution kinetics in heterogeneous aquifers

Estimates of contaminant fluxes from DNAPL sources as a function of time and DNAPL mass reduction are important to assess the long-term sustainability and costs of monitored natural attenuation and to determine the benefits of partial source removal. We investigate the accuracy of the upscaled mass transfer function (MTF) proposed by Parker and Park [Parker JC, Park E. Modeling field-scale dense nonaqueous phase liquid dissolution kinetics in heterogeneous aquifers. WRR 2004;40:W05109] to describe field-scale dissolved phase fluxes from DNAPL sources for a range of scenarios generated using high-resolution 3-D numerical simulations of DNAPL infiltration and long-term dissolved phase transport. The results indicate the upscaled MTF is capable of accurately describing field-scale DNAPL dissolution rates as a function of time. For finger-dominated source regions, an empirical mass depletion exponent in the MTF takes on values greater than one which results in predicted mass flux rates that decrease continuously with diminishing DNAPL mass over time. Lens-dominated regions exhibit depletion exponents less than one, which results in more step-function like mass flux versus time behavior. Mass fluxes from DNAPL sources exhibiting both lens- and finger-dominated subregions were less accurately described by the simple MTF, but were well described by a dual-continuum model of the same form for each subregion. The practicality of calibrating a dual-continuum model will likely depend on the feasibility of obtaining spatially resolved field measurements of contaminant fluxes or concentrations associated with the subregions using multilevel sampling or some other means.     

The influence of dimensionality on simulations of mass recovery from nonuniform dense non-aqueous phase liquid (DNAPL) source zones

The influence of model dimensionality on predictions of mass recovery from dense non-aqueous phase liquid (DNAPL) source zones in nonuniform permeability fields was investigated using a modified version of the modular three-dimensional transport simulator (MT3DMS). Thirty-two initial two- (2D) and three-dimensional (3D) tetrachloroethene–DNAPL source zone architectures, taken from a recent modeling study, were used as initial conditions for this analysis. Commonly employed source zone metrics were analyzed to determine differences between 2D and 3D predictions: (i) down-gradient flux-averaged contaminant concentration, (ii) reductions in contaminant mass flux through a down-gradient boundary, (iii) source zone ganglia-to-pool (GTP) ratio, and (iv) time required to achieve a remediation objective. 3D flux-averaged contaminant concentrations were approximately 3.5 times lower than concentrations simulated in 2D. This difference was attributed to dilution of the contaminant concentrations down gradient of the source zone. Contaminant flux reduction predictions for a given mass recovery were generally 5% higher in 3D simulations than in 2D simulations. The GTP ratio declined over time as mass was recovered in both 2D and 3D simulations. Although the source longevity (i.e., time required to achieve 99.99% mass recovery) differed between individual 2D and 3D realizations, the mean source longevity for the 2D and 3D simulation ensembles was within 2%. 2D simulations tended to over-predict the time required to achieve lower mass recovery levels (e.g. 50% mass recovery) due to a smaller contaminated area exposed to uncontaminated water. These findings suggest that ensemble averages of 2D numerical simulations of DNAPL migration, entrapment, dissolution, and mass recovery in statistically homogenous, nonuniform media may provide reasonable approximations to average behavior obtained using simulations conducted in fully three-dimensional domains.     

Carbon Isotope Fractionation of PCE and TCE During Dechlorination by Vitamin B12

Reductive dechlorination of perchloroethylene (PCE) and trichloroethylene (TCE) by vitamin B12 is an analogue of the microbial reductive dechlorination reaction and is presently being applied as a remediation technique. Stable carbon isotopic analysis, an effective and powerful tool for the investigation and monitoring of contaminant remediation, was used to characterize the isotopic effects of reductive dechlorination of PCE and TCE by vitamin B12 in laboratory microcosms. In laboratory experiments, 10 mg/L vitamin B12 degraded >90% of the initial 20 mg/L PCE with TCE, the primary product of PCE degradation, accounting for between 64% and 72% of the PCE degraded. In experiments with TCE, 147 mg/L vitamin B12 degraded >90% of the initial 20 mg/L TCE with cis -dichloroethene ( c DCE), the primary product of degradation accounting for between 30% and 35% of the TCE degraded. Degradation of both PCE and TCE exhibited first-order kinetics. Strong isotopic fractionation of the reactant PCE and of the reactant TCE was observed over the course of degradation. This fractionation could be described with a Rayleigh model using enrichment factors of −16.5%o and −15.8%o for PCE, and −17.2%o and −16.6%o for TCE. Fractionation was similar in all experiments, with a mean enrichment factor of −16.5%o ± 0.6%o. The occurrence of such large enrichment factors indicates that isotopic analysis can be used to monitor the dechlorination of PCE and TCE by vitamin B12 and remediation of ground water plumes. Evidence indicates that isotopic fractionation is taking place during complexation of the chlorinated ethenes to vitamin B12, as has been suggested for reductive dechlorination by zero valent iron. The differences between e values for this reaction and those observed for anaerobic biodegradation of the chlorinated ethenes suggest that there may be differences in the rate-determining step for these two processes.     

Dissolved Hydrogen Dynamics Associated with Emulsified Vegetable Oil Bioremediation of Chloroethenes

Emulsified vegetable oil (EVO) is widely used as a fermentable substrate to enhance the reductive dechlorination of chlorinated ethenes (CEs) in groundwater systems. The fermentation of EVO by naturally occurring bacteria produces molecular hydrogen (H₂) which acts as an electron donor driving microbially mediated reductive dechlorination. While dissolved H₂ drives much of the dechlorination associated with CE bioremediation, the dynamics of H₂ production and consumption associated with EVO addition to groundwater systems is seldom documented. The present study shows how H₂ concentrations changed over a 4-year period following EVO addition to a sandy coastal plain aquifer underlying Naval Air Station Pensacola, Florida, USA. Prior to EVO addition, H₂ concentrations at the site were in the range characteristic of Fe(III)-reducing conditions (0.2–0.6 nM). Following EVO addition, H₂ concentrations increased exponentially, peaking at approximately 25,000 nM. Hydrogen concentrations then began decreasing exponentially, and by 4 years after EVO addition had stabilized at 4.0 nM. That pattern suggests symbiotic cross-feeding between fermentative and respirative microbial populations resulting in a Gaussian rise and fall of H₂ concentrations. That, in turn, suggests while EVO biostimulation can temporarily increase H₂ concentrations to very high levels, those higher concentrations are unlikely to be sustained indefinitely.     

Chloroethene Biotransformation in the Presence of Different Sulfate Concentrations

This paper aims to reconcile discrepancies among reports of dechlorination performance in the presence of sulfate, by analyzing data from the literature, presenting results from laboratory experiments performed with mixed anaerobic microbial cultures, and synthesizing respective findings. A complete set of metrics for dechlorination progress was developed and used in the analysis of selected field and laboratory studies. When differences in site and experimental conditions are accounted for and definitions of dechlorination completeness are harmonized, the inverse relationship between dechlorination performance and sulfate concentration becomes clearer. This relationship was investigated in detail with laboratory experiments on mixed anaerobic microbial cultures enriched with the same concentration of trichloroethylene (TCE) and different sulfate concentrations, equal to near zero (considered as the baseline culture), 30, 400, and 1100 mg/L. In all experiments, sulfate reduction proceeded concurrently with dechlorination. The observed behavior was bimodal, indicating a transition in dechlorination performance between 30 and 400 mg/L. Under low donor to acceptor stoichiometry conditions, TCE dechlorination was incomplete in all experiments after 14 days, while the percentage of TCE moles reduced to vinyl chloride was lower by about 50% in the experiments with high sulfate concentrations. When donor was added in excess to stoichiometry needs for TCE reduction, TCE dechlorination was complete in the baseline culture, while only little ethene was detected in the high sulfate concentration cultures. When all studies are considered together, it appears that the presence of sulfate does not preclude complete dechlorination but rather delays it. Data analysis also suggests that the proposed upper limit of 500 mg/L for the range of initial sulfate concentration that is not problematic for dechlorination should be revised to a lower value.     

The effect of spontaneous gas expansion and mobilization on the aqueous-phase concentrations above a dense non-aqueous phase liquid pool

The spontaneous expansion and mobilization of discontinuous gas above dense non-aqueous-phase liquid (DNAPL) pools can affect the aqueous-phase concentrations of the DNAPL constituents above the pool. The results of an intermediate-scale, two-dimensional flow cell experiment showed that the discontinuous gas flow produced by spontaneous expansion, driven by the partitioning of 1,1,1-TCA from the surface of a DNAPL pool, resulted in detectable aqueous-phase concentrations of 1,1,1-TCA well above the pool surface. In comparison to a conventional model for DNAPL pool dissolution in the absence of a discontinuous gas phase, these concentrations were greater than expected, and were present at greater than expected elevations. Additionally, this study showed that the discontinuous gas flow produced transient behavior in the aqueous-phase concentrations, where the elevated concentrations occurred as short-term, pulse-like events. These results suggest that the spontaneous expansion and mobilization of discontinuous gas in DNAPL source zones could lead to the misdiagnosis of source zone architecture using aqueous concentration data, and that the transient nature of the elevated concentrations could further complicate the difficult task of source zone characterization.     

Comparison of alternative upscaled model formulations for simulating DNAPL source dissolution and biodecay

This paper compares the performance of analytical and numerical approaches for modeling DNAPL dissolution with biodecay. A solution derived from a 1-D advective transport formulation (“Parker” model) is shown to agree very closely with high resolution numerical solutions. A simple lumped source mass balance solution in which with decay is assumed proportional to DNAPL mass (“Falta1” model) over- or underpredicts aqueous phase biodecay depending on the magnitude of the exponential factor governing the relationship between dissolution rate and DNAPL mass. A modification of the Falta model that assumes decay proportional to the source exit concentration is capable of accurately simulating source behavior with strong aqueous phase biodecay if model parameters are appropriately selected or calibrated (“Falta2” model). However, parameters in the lumped models exhibit complex interdependencies that cannot be quantified without consideration of transport processes within the source zone. Combining the Falta2 solution with relationships derived from the Parker model was found to resolve these limitations and track the numerical model results. A method is presented to generalize the analytical solutions to enable simulation of partial mass removal with changes in source parameters over time due to various remedial actions. The algorithm is verified by comparison with numerical simulation results. An example application is presented that demonstrates the interactions of partial mass removal, enhanced biodecay, enhanced mass transfer and source zone flow reduction applied at various time periods on contaminant flux reduction. Increasing errors that arise in numerical solutions with coarse discretization and high decay rates are shown to be controlled by using an adjusted decay coefficient derived from the Parker analytical solution.     

Biostimulation and Bioaugmentation to Enhance Reductive Dechlorination of TCE in a Long‐Term Flow Through Column Study

Large laboratory columns (15.2 cm diameter, 183 cm long) were fed with groundwater containing trichloroethylene (TCE), were biostimulated and bioaugmented, and were monitored for over 7.5 years. The objective of the study was to observe how the selection of the carbon and energy source, i.e., whey, Newman Zone^® standard surfactant emulsified oil and Newman Zone nonionic surfactant emulsified oil, affected the rate and extent of dechlorination. Column effluent was monitored for TCE and its degradation products, redox indicators (nitrate‐N, Fe(II), sulfate), and changes in iron mineralogy. Total bacteria and Dehalococcoides mccartyi strains were quantified using q‐PCR. Complete dechlorination was only observed in the whey treated columns, occurring 1 year after bioaugmentation with addition of a culture known to dechlorinate TCE to ethene, and 3 years later in the non‐bioaugmented column. The addition of the emulsified oils with or without bioaugmentation resulted in dechlorination only through cis‐DCE and vinyl chloride. While Dehalococcoides mccartyi strains are the only known bacteria that can fully dechlorinate TCE, their presence, either natural or augmented, was not the sole determiner of complete dechlorination. The establishment of a supporting microbial community and biogeochemistry that developed with continuous feeding of whey, in addition to the presence of D. mccartyi, were necessary to support complete reductive dechlorination. Results confirm that careful selection of a biostimulant is critical to the success of TCE dechlorination in complex soil environments.     

Parameter estimation in nonlinear environmental problems

Popular parameter estimation methods, including least squares, maximum likelihood, and maximum a posteriori (MAP), solve an optimization problem to obtain a central value (or best estimate) followed by an approximate evaluation of the spread (or covariance matrix). A different approach is the Monte Carlo (MC) method, and particularly Markov chain Monte Carlo (MCMC) methods, which allow sampling from the posterior distribution of the parameters. Though available for years, MC methods have only recently drawn wide attention as practical ways for solving challenging high-dimensional parameter estimation problems. They have a broader scope of applications than conventional methods and can be used to derive the full posterior pdf but can be computationally very intensive. This paper compares a number of different methods and presents improvements using as case study a nonlinear DNAPL source dissolution and solute transport model. This depth-integrated semi-analytical model approximates dissolution from the DNAPL source zone using nonlinear empirical equations with partially known parameters. It then calculates the DNAPL plume concentration in the aquifer by solving the advection-dispersion equation with a flux boundary. The comparison is among the classical MAP and some versions of computer-intensive Monte Carlo methods, including the Metropolis–Hastings (MH) method and the adaptive direction sampling (ADS) method.     

A multiphase flow and multispecies reactive transport model for DNAPL-involved Compound Specific Isotope Analysis

This study presents a multiphase flow and multispecies reactive transport model for the simultaneous simulation of NAPL and groundwater flow, dissolution, and reactive transport with isotope fractionation, which can be used for better interpretation of NAPL-involved Compound Specific Isotope Analysis in 3D heterogeneous hydrogeologic systems. The model was verified for NAPL-aqueous phase equilibrium partitioning, aqueous phase multi-chain and multi-component reactive transport, and aqueous phase multi-component transport with isotope fractionation. Several illustrative examples are presented to investigate the effect of DNAPL spill rates, degradation rate constants, and enrichment factors on the temporal and spatial distribution of the isotope signatures of chlorinated aliphatic hydrocarbon groundwater plumes. The results clearly indicate that isotope signatures can be significantly different when considering multiphase flow within the source zone. A series of simulations indicate that degradation and isotope enrichment compete with dissolution to determine the isotope signatures in the source zone: isotope ratios remain the same as those of the source if dissolution dominates the reaction, while heavy isotopes are enriched in reactants along groundwater plume flow paths when degradation becomes dominant. It is also shown that NAPL composition can change from that of the injected source due to the partitioning of components between the aqueous and NAPL phases even when degradation is not allowed in NAPL phase. The three-dimensional simulation is presented to mechanistically illustrate the complexities in determining and interpreting the isotopic signatures with evolving DNAPL source architecture.     

Long-Term Evaluation of Mulch Biowall Performance to Treat Chlorinated Solvents

Permeable reactive barriers (PRBs), such as mulch biowalls, have been installed at numerous groundwater cleanup sites, and laboratory and field studies have demonstrated biotic and abiotic processes that degrade chlorinated volatile organic compounds (CVOCs) in groundwater passing through these engineered remedies. However, the longevity of mulch biowalls remains a fundamental research question. Soil and groundwater sampling at seven mulch biowalls at Altus Air Force Base (AFB) approximately 10 years after installation demonstrated the ongoing degradation of CVOCs. Trichloroethene was not detected in five of seven groundwater samples collected from the biowall despite upgradient detections above federal drinking water standards. Microbial sampling established the presence of key dechlorinating bacteria and the abundance of genes encoding specific enzymes for degradation, high methane concentrations, low sulfate concentrations, and negative oxidation-reduction potential, all indicative of highly reducing conditions within the biowalls and favorable conditions for CVOC destruction via microbial reductive dechlorination. High cellulose content (>79%) of the mulch, elevated total organic carbon (TOC) content in groundwater, and elevated potentially bioavailable organic carbon (PBOC) measurements in soil samples further supports an ongoing, long-lived source of carbon. These results demonstrate the ongoing and long-term efficacy of the mulch biowalls at Altus AFB. In addition, concentrations of bacteria, TOC, PBOC, and other geochemical parameters suggest a modest impact of the biowalls downgradient. The continued presence of CVOCs downgradient may be attributable to back diffusion from low-permeability shale. However, the biowalls continue to provide benefits by removing CVOCs in groundwater, thus reducing further CVOC loading to the downgradient, low-permeability strata.     

Mass Flux Analysis of Abiotic Tetrachloroethene Dense Nonaqueous Phase Liquid Pool Dissolution in a Heterogeneous Flow Environment

Porous aquifer materials are often characterized by layered heterogeneities that influence groundwater flow and present complexities in contaminant transport modeling. Such flow variations also have the potential to impact the dissolution flux from dense nonaqueous phase liquid (DNAPL) pools. This study examined how these heterogeneous flow conditions affected the dissolution of a tetrachloroethene (PCE) pool in a two-dimensional intermediate-scale flow cell containing coarse sand. A steady-state mass-balance approach was used to calculate the PCE dissolution rate at three different flow rates. As expected, aqueous PCE concentrations increased along the length of the PCE pool and higher flow rates decreased the aqueous PCE concentration in the effluent. Nonreactive tracer studies at two flow rates confirmed the presence of a vertical flow gradient, with the most rapid velocity located at the bottom of the tank. These results suggest that flow focusing occurred near the DNAPL pool. Effluent PCE concentrations and pool dissolution flux rates were compared to model predictions assuming local equilibrium (LE) conditions at the DNAPL pool/aqueous phase interface and a uniform distribution of flow. The LE model did not describe the data well, even over a wide range of PCE solubility and macroscopic transverse dispersivity values. Model predictions assuming nonequilibrium mass-transfer-limited conditions and accounting for vertical flow gradients, however, resulted in a better fit to the data. These results have important implications for evaluating DNAPL pool dissolution in the field where subsurface heterogeneities are likely to be present.