- Halogenated organic compounds have had widespread and massive applications in industry, agriculture, and private households, for example, as degreasing solvents, flame retardants and in polymer production. They are released to the environment through both anthropogenic and natural sources. The most common chlorinated solvents present as contaminants include tetrachloroethene (PCE, perchloroethene) and trichloroethene (TCE). These chlorinated solvents are problematic because of their health hazards and persistence in the environment, threatening human and environmental health. Microbial reductive dechlorination is emerging as a promising approach for the remediation of chlorinated solvents in aquifers. In microbial reductive dechlorination, specialized bacteria obtain energy for growth from metabolic dechlorination reactions that convert PCE to TCE, cis-1,2-dichloroethene (cDCE), vinyl chloride (VC), and finally to benign ethene. Field studies show incomplete dechlorination of PCE to ethene due to lack of electron donors or other populations competing for the electron donor.
Mathematical models are good tools to integrate the processes affecting the fate and transport of chlorinated solvents in the subsurface. This thesis explores the use of modeling to provide a better understanding of the reductive dehalogenation process of chlorinated solvents and their competition with other microorganisms for available electron donors in continuous flow systems such as a continuous stirred tank reactor (CSTR) and a continuous flow column. The model is a coupled thermodynamic and kinetic model that includes inhibition kinetics for the dechlorination reactions, thermodynamic constraints on organic acids fermentation and has incorporated hydrogen competition among microorganisms such as homoacetogenesis, sulfate reducers and ferric iron reducers. The set of equations are coupled to those required for modeling a CSTR. The system of model equations was solved numerically using COMSOL 3.5 a, which employs finite-element methods. The kinetic model was verified by simulation results compared to previously published models and by electron balances.
The simulation process progressed by simulating the anaerobic reductive dechlorination, coupled with thermodynamic limitation of electron donor fermentation in batch systems to the modeling of CSTR, and finally to simulate anaerobic reductive dechlorination in continuous flow column, aquifer column including the processes of advection, dispersion and sorption along with the microbial processes of dehalogenation, fermentation, iron and sulfate reduction. The simulations using the developed model captured the general trends of the chemical species, and a good job predicting the dynamics of microbial population responses either the CSTRs or continuous flow column.
Although, the kinetic of anaerobic dechlorination processes of chlorinated solvents in those systems have been researched in the past, little progress has been made towards understanding the combined effects of the dechlorination and thermodynamic constraints in continuous flow systems. This work provides a rigorous mathematical model for describing the coupled effects of these processes.