Reductive dechlorination of chlorinated aliphatic hydrocarbons by Fe(ii) in degradative solidification/stabilization
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This dissertation examines the applicability of the iron-based degradative solidification/stabilization (DS/S-Fe(II)) to various chlorinated aliphatic hydrocarbons (CAHs) that are common chemicals of concern at contaminated sites. The research focuses on the transformation of 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2,2-tetrachloro-ethane (1,1,2,2-TetCA) and 1,2-dichloroehtane (1,2-DCA) by Fe(II) in cement slurries. It also investigates the degradation of 1,1,1-TCA by a mixture of Fe(II), cement and three iron-bearing phyllosilicates. Transformation of 1,1,1-TCA and 1,1,2,2-TetCA by Fe(II) in 10% cement slurries was characterized using batch reactors. Dechlorination kinetics of 1,1,1-TCA and TCE* (TCE that was produced by transformation of 1,1,2,2-TetCA) was strongly dependent on Fe(II) dose, pH and initial target organic concentration. Degradation of target organics in DS/S-Fe(II) process was generally described by a pseudo-first-order rate law. However, saturation relationships between the rate constants and Fe(II) dose or between the initial degradation rates and target organic concentration were observed. These behaviors were properly described by a modified Langmuir-Hinshelwood kinetic model. This supports the working hypothesis of this research that reductive dechlorination of chlorinated ethanes occurs on the surface of active solids formed in mixtures of Fe(II) and cement. Transformation products for 1,1,1-TCA and 1,1,2,2-TetCA in mixtures of Fe(II) and cement were identified. The major product of the degradation of 1,1,1-TCA was 1,1-DCA, which indicates that the reaction followed a hydrogenolysis pathway. However, a small amount of ethane was also observed. TCE* was rapidly produced by degradation of 1,1,2,2-TetCA and is expected to undergo ÃÂ²-elimination to produce acetylene. Dechlorination of 1,1,1-TCA in suspension of Fe(II), cement and three soil minerals (biotite, vermiculite, montmorillonite) was characterized using batch reactors. A first-order rate model was generally used to describe the dechlorination kinetics of 1,1,1-TCA in this heterogeneous system. The rate constants for 1,1,1-TCA in mixtures of Fe(II), cement and soil minerals were influenced by soil mineral types, Fe(II) dose and the mass ratio of cement to soil mineral. It was demonstrated that structural Fe(II) and surface-bound Fe(II) in the soil minerals affect dechlorination kinetics and the effects vary with mineral types. Furthermore, it suggests that the reductant formed from Fe(II) and cement hydration components is also effective in systems that include soil minerals.
Jung, Bahng Mi (2005). Reductive dechlorination of chlorinated aliphatic hydrocarbons by Fe(ii) in degradative solidification/stabilization. Doctoral dissertation, Texas A&M University. Texas A&M University. Available electronically from