Abstract
Halogenated aliphatic compounds (HACs) can be reduced by iron sulfides in aqueous systems. Generally, the thermodynamics and kinetics of dehalogenation reactions are controlled by the mineralogical and particle surface characteristics of the iron sulfide, the composition of the HAC and reaction conditions such as component concentrations, pH and Eh. In this theoretical and experimental investigation of CCl4 and C2Cl6 reduction by FeS and FeS2, the roles of hydrophobic and hydrophilic sites on the iron sulfides were analyzed. Experimental data obtained through zeta potential measurements, were used along with the Gouy-Chapman model and the simple two-layer surface complexation model to relate iron sulfide surface hydroxyl densities to the degree of HAC dehalogenation. The surface hydroxyl site densities of FeS and FeS2 were found to be 0.11 sites/nm2 and 0.21 sites/nm2, respectively. During the dehalogenation reaction process, CCl4 was found to decrease to its first intermediate product CHCl3 within the first 20 hours followed by a slower process of conversion to CH2Cl2. The results also show that FeS is less hydrated (more hydrophobic) than FeS2. For CCl4 and C2Cl6, FeS is a better dehalogenator than FeS2. These results imply that particle surface hydrophobicity is a critical factor in surface-mediated dehalogenation of chlorinated compounds.
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Agrawal, A., Liang, L. and Tratnyek, P. G.: 1995, ‘Phenomena Affecting Remediation of Organic Groundwater Contaminants with Iron Metal at Solid-Water Interface’, Extended Abstract, American Chemical Society, Industrial and Engineering Chemistry Division, 54–55.
Burris, D. R., Campbell, T. J. and Manoranjan, V. S.: 1995, ‘Sorption of trichloroethylene and tetrachloroethylene in a batch reactive metallic iron-water system’, Env. Sci. Technol. 29, 2850–2855.
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’, ASCE J. Envir. Engr. 10, 1012–1019.
Butler, E. C. and Hayes, K. F.: 1998, ‘Effects of solution composition and pH on the reductive dechlorination of hexachloroethane by iron sulfide’, Env. Sci. Technol. 32, 1276–1284.
Butler, E. C. and Hayes, K. F.: 1999, ‘Kinetics of the transformation of trichloroethylene and tetrachloroethylene by iron sulfide’, Env. Sci. Technol. 33, 2021–2027.
Butler, E. C. and Hayes, K. F.: 2000, ‘Kinetics of the transformation of halogenated aliphatic compounds by iron sulfide. Env. Sci. Technol. 34, 422–429.
Cipollone, M. G., Wolfe, N. L. and Hassan, S. M.: 1995, ‘Kinetic studies on the use of metallic iron to reduce organic compounds in water under environmental conditions’, Natl. Meet.-Am. Chem. Soc., Div. Environ. Chem. 35, 812–814 (Abstr.).
Coracioglu, O. M. and Huang, C. P.: 1987, ‘The surface acidity and characterization of some commercial activated carbons’, Carbon, 25(4), 569–578.
Dahmke, A.: 1997, Aktualisierung der literaturstudie „Reaktive Wände”, pH-Redox-reaktive Wände. Landesanstalt für Umweltschutz, Baden-Würtemberg, texte und Berichte zur Altlastenbearbeitung, 33/97, Karlsruche.
Gillham, R. W., O'Hannesin, S. F. and Orth, W. S.: 1993, ‘Metal enhanced abiotic degradation of halogenated aliphatics: laboratory tests and field trials’, Proceedings of the 1993 Hazmat Central Conference, Chicago, IL, Mar 9–11.
Gillham, R. W.: 1995, ‘Resurgence of research concerning organic transformations enhanced by zero-valent metals and potential application in remediation of contaminated groundwater’, Natl. Meet.-Am. Chem. Soc., Div. Environ. Chem. 35, 691–694 (Abstr.).
Gotpagar, J. K., Grulke, E. A. and Bhattacharyya, D.: 1998, ‘Reductive dehalogenation of trichloroethylene: kinetic models and experimental verification’, J. Hazard. Mat. 62, 243–264.
Gotpagar, J., Lyuksyutov, S., Cohn, R., Grulke, E. and Bhattacharyya, D.: 1999, ‘Reductive dehalogenation of trichloroethylene with zero-valent iron: surface profiling microscopy and rate enhancement studies’, Langmuir 15, 8412–8420.
Hayes, K. F., Redden, G., Ela, W. and Leckie, J. O.: 1991, ‘Surface complexation models: An evaluation using FITEQL and oxides mineral titration data’, J. Colloid and Interface Sci. 142(2), 448–469.
Hochella, M. F., Jr. and White, A. F.: 1990, ‘In Mineral-Water Interface Geochemistry’, Reviews in mineralogy 23, Mineralogical Society of America, Washington, D.C.
Huang, C. P. and Stumm, W.: 1973, ‘Adsorption of cations on hydrous Al2O3’, J. Colloid and Interface Sci. 43(2), 409–414.
Huang, C. P., Hsieh, Y. S., Park, S. W. and Corapcioglu, M. O.: 1986, ‘Chemical interactions between heavy metal ions and hydrous solids’, Metal speciation, separation and recovery, in J. W. Patterson and R. Passino (eds.), Lewis, Boca Raton, Fla., pp. 437–465.
Hung, H. M. and Hoffmann, M. R.: 1998, ‘Kinetics and mechanism of the enhanced reductive degradation of CCl4 by elemental iron in the presence of ultrasound’, Env. Sci. Technol. 32, 3011–3016.
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’, J. Contam. Hydrol. 29, 379–398.
Matheson, L. J. and Tratnyek, P. G.: 1994, ‘Reductive dehalogenation of chlorinated methanes by iron metal’, Env. Sci. Technol. 28, 2045–2053.
McBride, M. B.: 1994, ‘ Environmental chemistry of soils’, Oxford Univ. Press, New York, 406 pp.
Park, S. W. and Huang, C. P.: 1987, ‘The surface acidity of hydrous CdS(s)’, J. Colloid and Interface Sci. 117(2), 431–441.
Noh, J. S. and Schwarz, J. A.: 1990, ‘Estimation of surface ionization constants for amphoteric solids’, J. Colloid and Interface Sci. 139(1), 139–148.
Puls, R. W., Powell, R. M. and Paul, C. J.: 1995, ‘In situ remediation of groundwater contaminated with chromate and chlorinated solvents using zero-valent iron, a field study’, Natl. Meet.-Am. Chem. Soc., Div. Environ. Chem. 35, 788–791 (Abstr.).
Ramamoorthy, S. and Ramamoorthy, S.: 1997, ‘ Chlorinated organic compounds in the environment’, Lewis Publishers, New York
Sivavec, T. M.: 1995, ‘Reductive dechlorination of chlorinated solvents by iron metal and iron sulfide minerals. Proceedings of IBC International Symposium on Biological Dehalogenation, Annapolis, MD, Oct 19. (Abstr.).
Sivavec, T. M. and Horney, D. P.: 1995, ‘Reductive dechlorination of chlorinated ethenes by iron metal’, Natl. Meet.-Am. Chem. Soc., Div. Environ. Chem. 35, 695–698 (Abstr.)
Kriegman-King, M. R. and Reinhard, M.: 1992, ‘Transformation of carbon tetrachloride in the presence of sulfide, biotite, and vermiculite’, Env. Sci. Technol. 26, 2198–2206.
Vogan, J. L., Gillham, R. W., O'Hannesin, S. F., Matulewicz, W. H. and Rhodes, J. E.: 1995, ‘Site specific degradation of VOCs in groundwater using zero valent iron’, Natl. Meet.-Am. Chem. Soc., Div. Environ. Chem. 35, 812–814 (Abstr.).
Vogel, T. M., Criddle, C. S. and McCarthy, P. L.: 1987, ‘Transformation of halogenated aliphatic compounds’, Env. Sci. Technol. 21, 722–736.
Weng, C. H., Huang, C. P., Member, ASCE, Allen, H. E. and Sanders, P. F.: 2001, ‘Cr(VI) adsorption onto hydrous concrete particles from groundwater’, J. Environ. Eng. 127(12), 1124–1131.
Yamane, C. L., Gallinatti, J. D., Szerdy, F. S., Delfino, T. A., Hankins, D. A. and Vogan, J. L.: 1995, ‘Installation of a subsurface groundwater treatment wall composed of granular zero-valent iron’, Natl. Meet.-Am. Chem. Soc., Div. Environ. Chem. 35, 792–795 (Abstr).
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Park, SW., Kim, SK., Kim, JB. et al. Particle Surface Hydrophobicity and the Dechlorination of Chloro-Compounds by Iron Sulfides. Water Air Soil Pollut: Focus 6, 97–110 (2006). https://doi.org/10.1007/s11267-005-9016-z
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DOI: https://doi.org/10.1007/s11267-005-9016-z