Abstract
Optimal design of zerovalent iron-based permeable reactive barriers requires a complete understanding of dechlorination kinetics and mechanism. The effect of other ambient constituents, which may retard or enhance the dechlorination processes, should be considered. Literature has revealed that reduction of chlorinated compounds occurs on the iron surface and the reaction rate is limited by surface processes, rather than transport processes. Adsorption onto the surface can take place on both reactive sites that are responsible for the reductive dechlorination, and nonreactive sites that only sequester the contaminants. This chapter explores a model based on the assumptions that adsorption equilibrium on the two types of surface sites is always maintained, but the reduction rate is directly proportional to the amount sorbed onto reactive sites only. Numerical solutions are obtained to illustrate the effect of coadsorbates on the adsorption and reduction of chlorinated compounds under this mechanistic framework.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Bibliography
Allen-King R. M., Halket R. M., and Burris D. R. (1997) Reductive transformation and sorption of cis-and trans-1,2-dichloroethylene in a metallic iron-water system. Environmental Toxicology and Chemistry 16(3), 424–429.
Arnold W. A. and Robert A. L. (1998) Pathways of chlorinated ethylene and chlorinated acetylene reaction with Zn(0). Environmental Science & Technology 32(19), 3017–3025.
Burris D. R., Allen-King R. M., Manoranjan V. S., Campbell T. J., Loraine G. A., and Deng B. (1998) Chlorinated ethene reduction by cast iron: sorption and mass transfer. Journal of Environmental Engineering 124(10), 1012–1019.
Burris D. R., Campbell T. J., and Manoranjan V. S. (1995) Sorption of trichloroethylene and trichloroethylene in a batch reactive metallic iron-water system. Environmental Science & Technology 29(11), 2850–2855.
Campbell T. J., Burris D. R., Roberts A. L., and Wells R. J. (1997) Trichloroethylene and tetrachloroethylene reduction in a metallic iron-water-vapor batch system. Environmental Toxicology and Chemistry 16(4), 625–630.
Cherry J. A., Feenstra S., and Mackay D. M. (1996) Concepts for the remediation of sites contaminated with dense non-aqueous phase liquids (DNAPLs). In Dense Chlorinated Solvents and Other DNAPLs in Groundwater (ed. J. F. Pankow and J. A. Cherry), pp. 475–506. Waterloo Press.
Deng B., Burris D. R., and Campbell T. J. (1999) Reduction of vinyl chloride in metallic iron-water systems. Environmental Science & Technology 33(15), 2651–2656.
Deng B., Campbell T. J., and Burris D. R. (1997) Hydrocarbon Formation in Metallic Iron/Water Systems. Environmental Science & Technology 31(4), 1185–1190.
Deng B., Hu S., and Burris D. R. (1998) Effect of iron corrosion inhibitors on trichloroethylene reduction. In Physical, Chemical, and Thermal Technologies (ed. G. B. Wickramanayake and R. R. Hinchee), pp. 341–346. Battelle Press.
EPA. (1998) Permeable Reactive Barrier Technologies for Contaminant Remediation. United States Environmental Protection Agency. EPA/600/R-98/125.
Focht R., Vogan J., and O’Hannesin S. (1996) Field application of reactive iron walls for in-site degradation of volatile organic compounds in groundwater. Remediation (Summer), 81–94.
Gavaskar A. R., Gupta N., Sass B. M., Janosy R. J., and O’Sullivan D. (1998) Permeable Barriers for Groundwater Remediation. Battelle Press.
Gillham R. W. and O’Hannesin S. F. (1994) Enhanced degradation of halogenated aliphatics by zero-valent iron. Ground Water 32(6), 958–967.
Glod G., Angst W., Holliger C., and Schwarzenbach R. P. (1997) Corrinoid-mediated reduction of tetrachloroethene, trichloroethene, and trichlorofluoroethene in homogeneous aqueous solution: reaction kinetics and reaction mechanisms. Environmental Science & Technology 31(1), 253–260.
Gossett, J. M. (1987) Measurement of Henry’s Law constants for C1 and C2 chlorinated hydrocarbons. Environ. Sci. Technol. 21, 202–208.
Hu S. (1999) Reductive Dechlorination of Trichloroethylene by Metallic Iron: Effects of Iron Corrosion and Corrosion Inhibition. Master Thesis, New Mexico Institute of Mining and Technology.
Johnson T. L., Fish W., Gorby Y. A., and Tratnyek P. G. (1998) Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface. Journal of Contaminant Hydrology 29, 379–398.
Johnson T. L., Scherer M. M., and Tratnyek P. G. (1996) Kinetics of halogenated organic compound degradation by iron metal. Environ. Sci. Technol. 30(8), 2634–2640.
Lasaga A. C. (1981) Transition state theory. In Kinetics of Geochemical Processes, Vol. 8 (ed. A. C. Lasaga and R. J. Kirkpatrick), pp. 135–169. Mineralogical Society of American.
Mackay D. M. and Cherry J. A. (1989) Groundwater contamination: pump and treat remediation. Environmental Science & Technology 23, 630–636.
Matheson L. J. and Tratnyek P. G. (1994) Reductive dechlorination of chlorinated methanes by iron metal. Environmental Science & Technology 28(12), 2045–2053.
NRC N. R. C. (1994) Alternatives for Ground Water Cleanup. National Academy Press.
Orth W. S. and Gillham R. W. (1996) Dechlorination of trichloroethylene in aqueous solution using Fe0. Environmental Science & Technology 30(1), 66–71.
Prigogine I. (1967) Introduction to Thermodynamics of Irreversible Processes. Wiley-Interscience.
Reynolds G. W., Hoff J. T., and Gillham R. W. (1990) Sampling bias caused by materials used to monitor halocarbons in groundwater. Environmental Science & Technology 24(1), 135–142.
Roberts L. A., Totten L. A., Arnold W. A., Burris D. R., and Campbell T. J. (1996) Reductive elimination of chlorinated ethylenes by zero-valent metals. Environmental Science & Technology 30(8), 2654–2659.
Scherer M. M, Westall J. C, ZiomekMoroz M, Tratnyek P. G, (1997) Kinetics of carbon tetrachloride reduction at an oxide-free iron electrode. Environmental Science & Technology 31(8) pp. 2385–2391.
Senzaki T. and Kumagai Y. (1988) Removal of chlorinated organic compounds from wastewater by reduction process: II. Treatment of trichloroethylene with iron powder. Kogyo Yosui 357, 2–7.
Sivavec T. M. and Horney D. P. (1997) Reduction of chlorinated solvents by Fe(II) minerals, Preprints of ACS annual meeting-Division of Environmental Chemistry, San Francisco, CA. 115–117.
Stumm W. and Sulzberger B. (1992) The cycling of iron in natural environments: consideration based on laboratory studies of heterogeneous redox processes. Geochimica et Cosmochimica Acta 56, 3233–3257.
Su C. and Puls R. W. (1999) Kinetics of trichloroethylene reduction by zerovalent iron and tin: pretreatment effect, apparent activation energy, and intermediate products. Environmental Science & Technology 33(1), 163–168.
Sweeny K. H. (1979) Reductive degradation treatment of industrial and municipal wastewaters. Water Reuse Symposium, 1487–1497.
Sweeny K. H. (1981) Reductive treatment of industrial wastewaters. I. Process description. AIChE Symp. Ser., 67–71.
Tratnyek P. G. (1996) Putting corrosion to use: remediating contaminated groundwater with zero-valent metals. Chemistry & Industry (1), 499–503.
Tratnyek P. G. and Scherer M. M. (1998) The effect of natural organic matter on reduction by zero-valent iron, Preprints of ACS annual meeting-Division of Environmental Chemistry, Boston, MA, 125–126.
Vogel T. M., Criddle C. S., and McCarty P. L. (1987) Transformations of halogenated aliphatic compounds. Environmental Science & Technology 21(8), 722–736.
Wilkins R. G. (1991) Kinetics and Mechanism of Reactions of Transition Metal Complexes. VCH.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2002 Kluwer Academic Publishers
About this chapter
Cite this chapter
Deng, B., Hu, S. (2002). Reductive Dechlorination of Chlorinated Solvents on Zerovalent Iron Surfaces. In: Smith, J.A., Burns, S.E. (eds) Physicochemical Groundwater Remediation. Springer, Boston, MA. https://doi.org/10.1007/0-306-46928-6_7
Download citation
DOI: https://doi.org/10.1007/0-306-46928-6_7
Publisher Name: Springer, Boston, MA
Print ISBN: 978-0-306-46569-7
Online ISBN: 978-0-306-46928-2
eBook Packages: Springer Book Archive