Review of reactive kinetic models describing reductive dechlorination of chlorinated ethenes in soil and groundwater.

Reductive dechlorination is a major degradation pathway of chlorinated ethenes in anaerobic subsurface environments, and reactive kinetic models describing the degradation process are needed in fate and transport models of these contaminants. However, reductive dechlorination is a complex biological process, where many microbial populations including dechlorinating, fermentative, methanogenic, iron and sulfate reducing, interact. In this article the modeling approaches and the experimental data needed to calibrate them are reviewed, classified, and discussed. Model approaches considered include first order kinetics, Monod kinetics to describe sequential reductive dechlorination and bacterial growth, and metabolic models which simulate fermentation and redox processes interacting with reductive dechlorination processes. The review shows that the estimated kinetic parameters reported vary over a wide range, and that experimental microbial data are scarce. Very few studies have been performed evaluating the influence of sulfate and iron reduction, and contradictory conclusions on the interaction of redox processes with reductive dechlorination have been reported. The modeling approaches for metabolic reductive dechlorination employing different descriptions of the interaction between redox and dechlorination processes and competition for hydrogen are classified. The current concepts lead to different results, suggesting a need for further investigations on the interactions between the microbial communities performing dechlorination and redox processes, including the establishment of biomarkers quantifying dechlorination, and on geochemical characterization. Finally, the relevance of laboratory data and the development of practical modeling tools for field applications are discussed.

Is there an environmental benefit from remediation of a contaminated site? Combined assessments of the risk reduction and life cycle impact of remediation.

A comparative life cycle assessment is presented for four different management options for a trichloroethene-contaminated site with a contaminant source zone located in a fractured clay till. The compared options are (i) long-term monitoring (ii) in-situ enhanced reductive dechlorination (ERD), (iii) in-situ chemical oxidation (ISCO) with permanganate and (iv) long-term monitoring combined with treatment by activated carbon at the nearby waterworks. The life cycle assessment included evaluation of both primary and secondary environmental impacts. The primary impacts are the local human toxic impacts due to contaminant leaching into groundwater that is used for drinking water, whereas the secondary environmental impacts are related to remediation activities such as monitoring, drilling and construction of wells and use of remedial amendments. The primary impacts for the compared scenarios were determined by a numerical risk assessment and remedial performance model, which predicted the contaminant mass discharge over time at a point of compliance in the aquifer and at the waterworks. The combined assessment of risk reduction and life cycle impacts showed that all management options result in higher environmental impacts than they remediate, in terms of person equivalents and assuming equal weighting of all impacts. The ERD and long-term monitoring were the scenarios with the lowest secondary life cycle impacts and are therefore the preferred alternatives. However, if activated carbon treatment at the waterworks is required in the long-term monitoring scenario, then it becomes unfavorable because of large secondary impacts. ERD is favorable due to its low secondary impacts, but only if leaching of vinyl chloride to the groundwater aquifer can be avoided. Remediation with ISCO caused the highest secondary impacts and cannot be recommended for the site.

Upscaled modeling of complex DNAPL dissolution.

A straightforward, upscaled DNAPL mass dissolution model is developed using relatively simple input consisting of characteristic dimensions and saturations of a DNAPL accumulation. Multiple accumulations are aggregated into a single source zone volume. Physically, the dissolution process is a combination of flow through the mass (advective component) and flow around the mass (dispersive component). The contribution of each component is based on initial characteristic length scales and the average initial saturation. Changes over time with the depletion of mass are captured with a changing relative permeability and a power law relationship for the fraction of initial mass remaining. The utility of the upscaled process model is demonstrated with data from three studies: numerical simulation of multiple pools, two-dimensional test cell experiments with mixed architecture and with heterogeneous soil, and a controlled field study of multicomponent DNAPL release and depletion. Use of the model successfully reproduced the observed multistage mass discharge in each study and illuminated the governing processes. The power law exponent was relatively constant for the various conditions and relative permeability changes were integral to the success. The numerical and experimental studies were run to complete mass depletion which the upscaled model matched. The input parameters are minimal and are found in typical DNAPL source zone characterization data.

Development and sensitivity analysis of a fully kinetic model of sequential reductive dechlorination in groundwater.

A fully kinetic biogeochemical model of sequential reductive dechlorination (SERD) occurring in conjunction with lactate and propionate fermentation, iron reduction, sulfate reduction, and methanogenesis was developed. Production and consumption of molecular hydrogen (H(2)) by microorganisms have been modeled using modified Michaelis-Menten kinetics and has been implemented in the geochemical code PHREEQC. The model have been calibrated using a Shuffled Complex Evolution Metropolis algorithm to observations of chlorinated solvents, organic acids, and H(2) concentrations in laboratory batch experiments of complete trichloroethene (TCE) degradation in natural sediments. Global sensitivity analysis was performed using the Morris method and Sobol sensitivity indices to identify the most influential model parameters. Results show that the sulfate concentration and fermentation kinetics are the most important factors influencing SERD. The sensitivity analysis also suggests that it is not possible to simplify the model description if all system behaviors are to be well described.

Evaluation of bioaugmentation with entrapped degrading cells as a soil remediation technology.

Soil augmentation with microbial degraders immobilized on carriers is evaluated as a potential remediation technology using a mathematical model that includes degradation within spatially distributed carriers and diffusion or advection-dispersion as contaminant mass transfer mechanisms. The total volume of carriers is a critical parameter affecting biodegradation performance. In the absence of advection, 320 and 20 000 days are required to mineralize 90% of the herbicide linuron by Variovorax sp. SRS16 encapsulated in 2 mm beads with 5 and 20 mm spacings, respectively. Given that many pesticide degraders have low intrinsic degradation rates and that only limited carrier to soil volume ratios are practically feasible, bioaugmented soils are characterized by low effective degradation rates and can be considered fully mixed. A simple exponential model is then sufficient to predict biodegradation as verified by comparisons with published experimental data. By contrast, the full spatially distributed model is needed to adequately model the degradation of faster degrading contaminants such as naphthalene and benzene which can be mass-transfer limited. Dimensionless Damköhler numbers are proposed to determine whether the spatially distributed model is required. Results show that field scale applications of immobilized degraders will be limited by the amount of carriers required to reach acceptable degradation rates.

Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes.

The use of compound specific multi-isotope approach (C and Cl) in the characterization of a chlorinated ethenes contaminated fractured aquifer allows the identification of several sources and contaminant plumes, as well as the occurrence of biodegradation and mixing processes. The study site is located in Spain with contamination resulting in groundwater concentrations of up to 50mg/L of trichloroethene (TCE), the most abundant chlorinated ethene, and 7 mg/L of tetrachloroethene (PCE). The potential sources of contamination including abandoned barrels, an underground tank, and a disposal lagoon, showed a wide range in δ(13)C values from -15.6 to -40.5‰ for TCE and from -18.5 to -32.4‰ for PCE, allowing the use of isotope fingerprinting for tracing of the origin and migration of these contaminants in the aquifer. In contrast, there is no difference between the δ(37)Cl values for TCE in the contaminant sources, ranging from +0.53 to +0.66‰. Variations of δ(37)Cl and δ(13)C in the different contaminant plumes were used to investigate the role of biodegradation in groundwater. Moreover, the isotopic data were incorporated into a reactive transport model for determination of whether the isotope pattern observed downstream from the tank's source could be explained by the simultaneous effect of mixing and biodegradation. The results demonstrate that a multi-isotope approach is a valuable tool for characterization of complex sites such as fractured bedrock aquifer contaminated by multiple sources, providing important information which can be used by consultants and site managers to prioritize and design more successful remediation strategies.

The impact of bioaugmentation on dechlorination kinetics and on microbial dechlorinating communities in subsurface clay till.

A molecular study on how the abundance of the dechlorinating culture KB-1 affects dechlorination rates in clay till is presented. DNA extracts showed changes in abundance of specific dechlorinators as well as their functional genes. Independently of the KB-1 added, the microbial dechlorinator abundance increased to the same level in all treatments. In the non-bioaugmented microcosms the reductive dehalogenase gene bvcA increased in abundance, but when KB-1 was added the related vcrA gene increased while bvcA genes did not increase. Modeling showed higher vinyl-chloride dechlorination rates and shorter time for complete dechlorination to ethene with higher initial concentration of KB-1 culture, while cis-dichloroethene dechlorination rates were not affected by KB-1 concentrations. This study provides high resolution abundance profiles of Dehalococcoides spp. (DHC) and functional genes, highlights the ecological behavior of KB-1 in clay till, and reinforces the importance of using multiple functional genes as biomarkers for reductive dechlorination.

A conceptual model linking functional gene expression and reductive dechlorination rates of chlorinated ethenes in clay rich groundwater sediment.

We used current knowledge of cellular processes involved in reductive dechlorination to develop a conceptual model to describe the regulatory system of dechlorination at the cell level; the model links bacterial growth and substrate consumption to the abundance of messenger RNA of functional genes involved in the dechlorination process. The applicability of the model was tested on a treatability study of biostimulated and bioaugmented microcosms. Using quantitative real time PCR, high-resolution expression profiles of the functional reductive dehalogenase genes bvcA and vcrA were obtained during two consecutive dechlorination events of trichlorethene, cis-dichlorethene and vinyl chloride. Up-regulation of the bvcA (for the biostimulated microcosms) and vcrA (for the bioaugmented microcosms) gene expression fitted well with high rates of dechlorination of vinyl chloride, while no known transcripts could be measured during trichloroethene and cis-dichlorethene dechlorination. Maximum concentrations of 2.1 and 1.7 transcripts per gene of the bvcA and vcrA genes, respectively, were measured at the same time points as maximum dechlorination rates were observed. The developed model compared well with the experimental data for both biostimulated and bioaugmented microcosms under non-steady state conditions and was supported by results from a recently published study under steady state conditions.

A remediation performance model for enhanced metabolic reductive dechlorination of chloroethenes in fractured clay till.

A numerical model of metabolic reductive dechlorination is used to describe the performance of enhanced bioremediation in fractured clay till. The model is developed to simulate field observations of a full scale bioremediation scheme in a fractured clay till and thereby to assess remediation efficiency and timeframe. A relatively simple approach is used to link the fermentation of the electron donor soybean oil to the sequential dechlorination of trichloroethene (TCE) while considering redox conditions and the heterogeneous clay till system (clay till matrix, fractures and sand stringers). The model is tested on lab batch experiments and applied to describe sediment core samples from a TCE-contaminated site. Model simulations compare favorably to field observations and demonstrate that dechlorination may be limited to narrow bioactive zones in the clay matrix around fractures and sand stringers. Field scale simulations show that the injected donor is expected to be depleted after 5 years, and that without donor re-injection contaminant rebound will occur in the high permeability zones and the mass removal will stall at 18%. Long remediation timeframes, if dechlorination is limited to narrow bioactive zones, and the need for additional donor injections to maintain dechlorination activity may limit the efficiency of ERD in low-permeability media. Future work should address the dynamics of the bioactive zones, which is essential to understand for predictions of long term mass removal.

A risk assessment tool for contaminated sites in low-permeability fractured media.

A risk assessment tool for contaminated sites in low-permeability fractured media is developed, based on simple transient and steady-state analytical solutions. The discrete fracture (DF) tool, which explicitly accounts for the transport along fractures, covers different source geometries and history (including secondary sources) and can be applied to a wide range of compounds. The tool successfully simulates published data from short duration column and field experiments. The use for risk assessment is illustrated by three typical risk assessment case studies, involving pesticides, chlorinated solvents, benzene and MTBE. The model is compared with field data and with results from a simpler approach based on an Equivalent Porous Media (EPM). Risk assessment conclusions of the DF and EPM approaches are very different due to the early breakthrough, long term tailing, and lower attenuation due to degradation associated with fractured media. While the DF tool simulates the field data, it is difficult to conclude that the DF model is superior to an EPM model because of a lack of long term monitoring data. However, better agreement with existing field data by the DF model using observed physical fracture parameters favors the use of this model over the EPM model for risk assessments.

Modeling multi-component transport and enhanced anaerobic dechlorination processes in a single fracture-clay matrix system.

Clayey tills contaminated with chlorinated solvents are a threat to groundwater and are difficult to remediate. A numerical model is developed for assessing leaching processes and for simulating the remediation via enhanced anaerobic dechlorination. The model simulates the transport of a contaminant in a single fracture-clay matrix system coupled with a reactive model for anaerobic dechlorination. The model takes into account microbially driven anaerobic dechlorination, where sequential Monod kinetics with competitive inhibition is used to model the reaction rates, and degradation is localized to account for potential pore size limitations on microbial entry to the clay matrix. The model is used to assess the distribution of TCE and its daughter products in the clay matrix and the concentration of the different compounds at the outlet of the fracture. The time frame for complete cleanup and the contaminant flux out of the clay system are assessed for different distributions of microbial degradation. Results from a set of scenarios show that time to remove 90% of the initial mass is halved when dechlorination occurs in a 5cm reaction zone in the clay at the fracture-matrix interface (from 419 to 195years) and decreases by an order of magnitude when dechlorination occurs in the entire matrix (to 32years). The fracture spacing and the microbial parameters are shown to be the critical parameter for estimation of time frames depending on the system in question. Generally, the system is more sensitive to the physical processes, mainly diffusion in the matrix, than to the biogeochemical processes, when dechlorination is assumed to take place in a limited reaction zone only. The inclusion of sequential dechlorination in clay fracture transport models is crucial, as the contaminant flux to the aquifer will increase as a result of degradation due to the higher mobility of the formed daughter products DCE and VC. The model is used to examine the relationship between flux reduction and mass removal for fractured clay systems.

Field evaluation of biological enhanced reductive dechlorination of chloroethenes in clayey till.

The performance of enhanced reductive dechlorination (ERD) for in situ remediation of cis-1,2-dichloroethene (cDCE) and vinyl chloride in clayey till was investigated in a pilot test. A dilute groundwater solution containing emulsified soybean oil and Dehalococcoides bacteria was injected into a sand-filled hydraulic fracture. Fermentation of the ERD solution caused the establishment of a dechlorinating bioactive zone in the fracture within 1 month of injection. By 148 days, all the cDCE in the fracture was dechlorinated to ethene. Analysis of a clay core from Day 150 indicated that electron donor and fermentation products diffused from the fracture at least 10 cm into clay and that stimulated dechlorination occurred in the clay in the presence of Dehalococcoides (7.9.10(4) cells g(-1)). Comparison of chloroethene profiles in the Day 150 core to modeled diffusion profiles indicated degradation occurred in a bioactive zone extending approximately 5 to 6 cm into the clay matrix. These data suggest that a bioactive zone established in a sand-filled fracture can expand into the adjacent clayey till matrix and facilitate mass transfer from the matrix to the bioactive zone. These findings offer promise for ERD and support further development of methods for deploying ERD in clayey till and other low-permeability deposits.