Chemistry of Modified Fenton’s Reagent (Catalyzed Propagations–CHP) for In Situ Soil and Groundwater Remediation
Publication: Journal of Environmental Engineering
Volume 131, Issue 4
Abstract
The use of modified Fenton’s reagent, or catalyzed propagations (CHP), has become increasingly popular for the in situ and ex situ treatment of surface soils and the in situ remediation of the subsurface. The process is based on the catalyzed decomposition of hydrogen peroxide by soluble iron, iron chelates, or iron minerals to generate the strong oxidant hydroxyl radical as well as other reactive oxygen species. Some of these species function as reductants and nucleophiles and may be responsible for the enhanced treatment of sorbed and nonaqueous phase liquid (NAPL) contaminants that is sometimes observed in the field. This paper serves as a review of the process chemistry of CHP; the goal is to provide researchers and practitioners with fundamental concepts that will aid in applying the CHP process to soil and groundwater contamination. Although the importance of well placement and the method of reagent injection must be considered in CHP remediation, understanding and promoting the most effective process chemistry is essential to successful soil and groundwater remediation.
Get full access to this article
View all available purchase options and get full access to this article.
References
Babbs, C. F., and Griffin, D. W. (1989). “Scatchard analysis of methane sulfinic acid production from dimethyl sulfoxide: A method to quantify hydroxyl radical formation in physiologic systems.” Free Radic Biol. Med., 6(5), 493–503.
Buyuksonmez, F., Hess, T. F., Crawford, R. L., and Watts, R. J. (1998). “Toxic effects of modified Fenton reactions on Xanthobacter flavus FB71.” Appl. Environ. Microbiol., 64(12), 3759–3764.
Buyuksonmez, F., Hess, T. F., Crawford, R. L., Paszczynski, A., and Watts, R. J. (1999). “Optimization of simultaneous chemical and biological mineralization of perchloroethylene (PCE).” Appl. Environ. Microbiol., 65(8), 2784–2788.
Chang, P. B. L., and Young, T. M. (2000). “Kinetics of methyl tert-butyl ether degradation and by-product formation during UV/hydrogen peroxide water treatment.” Water Res., 34(8), 2233–2240.
Chou, S. S., and Huang, C. P. (1999). “Application of a supported iron oxyhydroxide catalyst in oxidation of benzoic acid by hydrogen peroxide.” Chemosphere, 38(12), 2719–2731.
Environmental Security Technology Certification Program (ESTCP). (1999). Technology status review: In situ oxidation, Environmental Security Technology Certification Program, Arlington, Va.
Fenton, H. J. H. (1894). “Oxidation of tartaric acid in presence of iron.” J. Chem. Soc., 65, 899–910.
Feuerstein, W., Gilbert, E., and Eberle, S. H. (1981). “Model experiments for the oxidation of aromatic compounds by hydrogen peroxide in wastewater treatment.” Vom Wasser, 56(1), 35–54.
Gates, D. D., and Siegrist, R. L. (1995). “In situ chemical oxidation of trichloroethylene using hydrogen peroxide.” J. Environ. Eng., 121(9), 639–644.
Haag, W. R., and Yao, C. (1992). “Rate constants for reaction of hydroxyl radicals with several drinking water contaminants.” Environ. Sci. Technol., 26(6), 1005–1013.
Haber, F., and Weiss, J. (1934). “The catalytic decomposition of hydrogen peroxide by iron salts.” Proc. R. Soc. London, A147, 332–351.
Haeri-McCaroll, T. M. (1994). “The use of catalyzed hydrogen peroxide to oxidize chlorobenzenes in soil.” MS thesis, Washington State Univ., Pullman, Wash.
Hagiwara, K. (1984). “Treatment of wastewater containing nondecomposable organic compounds.” JETI, 32(1), 79–82.
Hoigne, J., and Bader, H. (1978). “Ozonation of water: Kinetics of oxidation of ammonia by ozone and hydroxyl radicals.” Environ. Sci. Technol., 12(1), 79–84.
Howsawkeng, J., et al. (2001). “Evidence for simultaneous abiotic-biotic oxidations in a microbial-Fenton’s system.” Environ. Sci. Technol., 35(12), 2845–2850.
Huang, H. H., Lu, M. C., and Chen, J. N. (2001). “Catalytic decomposition of hydrogen peroxide and 2-chlorophenol with iron oxides.” Water Res., 35(9), 2291–2299.
Huling, S. G., Arnold, R. G., Sierka, R. A., and Miller, M. R. (1998). “Measurement of hydroxyl radical activity in a soil slurry using the spin trap alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone.” Environ. Sci. Technol., 32(21), 3436–3441.
Huling, S. G., Arnold, R. G., Sierka, R. A., and Miller, M. R. (2001). “Influence of peat on Fenton oxidation.” Water Res., 35(7), 1687–1694.
Hunt, J. R., Sitar, N., and Udell, K. S. (1988). “Nonaqueous phase liquid transport and cleanup. I: Analysis of mechanisms.” Water Resour. Res., 24(5), 1247–1258.
Kakarla, P., and Watts, R. J. (1997). “Depth of Fenton-like oxidation in remediation of surface soils.” J. Environ. Eng., 123(1), 11–17.
Kao, C. M., and Wu, M. J. (2000). “Enhanced TCDD degradation by Fenton’s reagent preoxidation.” J. Hazard. Mater., 74(3), 197–211.
Kawahara, F. K., et al. (1995). “Polynuclear aromatic hydrocarbon (PAH) release from soil during treatment with Fenton’s reagent.” Chemosphere, 31(9), 4131–4142.
Khan, A. J., and Watts, R. J. (1996). “Mineral-catalyzed peroxidation of tetrachloroethylene.” Water, Air, Soil Pollut., 88(3–4), 247–260.
Kitao, T., Kiso, Y., and Yahashi, R. (1982). “Studies on the mechanism of decolorization with Fenton’s reagent.” Mizu Shori Gijutsu, 23(8), 1019–1026.
Kwan, W. P., and Voelker, B. M. (2003). “Rates of hydroxyl radical generation and organic compound oxidation in mineral-catalyzed Fenton-like systems.” Environ. Sci. Technol., 37(6), 1150–1158.
Lee, S. H., and Carberry, J. B. (1992). “Biodegradation of PCP enhanced by chemical oxidation pretreatment.” Water Res., 64(5), 682–690.
Lee, B. D., and Hosomi, M. (2001). “Fenton oxidation of ethanol-washed distillation-concentrated benzo(A)pyrene: Reaction product identification and biodegradability.” Water Res., 35(9), 2314–2319.
Lee, B. D., Hosomi, M., and Murakami, A. (1998). “Fenton oxidation with ethanol to degrade anthracene into biodegradable 9,10-anthraquinon: A pretreatment method for anthracene-contaminated soil.” Water Sci. Technol., 38(7), 91–97.
Lin, S. S., and Gurol, M. D. (1996). “Heterogeneous catalytic oxidation of organic compounds by hydrogen peroxide.” Water Sci. Technol., 34(9), 57–64.
Lin, S. S., and Gurol, M. D. (1998). “Catalytic decomposition of hydrogen peroxide on iron oxide: Kinetics, mechanisms, and implications.” Environ. Sci. Technol., 32(10), 1417–1423.
Lindsey, M. E., and Tarr, M. A. (2000a). “Quantitation of hydroxyl radical during Fenton oxidation following a single addition of iron and peroxide.” Chemosphere, 41(3), 409–417.
Lindsey, M. E., and Tarr, M. A. (2000b). “Inhibited hydroxyl radical degradation of aromatic hydrocarbons in the presence of dissolved fulvic acid.” Water Res., 34(8), 2385–2389.
Luzzatto, E., Cohen, H., Stockheim, C., Wieghardt, K., and Meyerstein, D. (1995). “Reactions of low-valent transition-metal complexes with hydrogen peroxide. Are they Fenton-like or not. 4. The case of Fe(II)L, , HEDTA, and TCMA.” Free Radical Res., 23(5), 453–463.
Martens, D. A., and Frankenberger, Jr., W. T. (1994). “Feasibility of in situ chemical oxidation of refractile chlorinatic organics by hydrogen peroxide-generated oxygen radicals in soil.” Emerging Technology for Bioremediation of Metals, J. L. Means and R. E. Hinchee, eds., 2nd Ed., CRC, Boca Raton, Fla., 74–84.
Matsumoto, Y., Totsuka, Y., and Kenichi, S. (1985). “Biological treatment of slightly degradable wastewater. Treatment of PVA wastewater.” Shizuoka-ken kogyo Gijutsu Senta Kenkyu Hokoku, 29(1), 53–60.
Miller, C. M., Valentine, R. L., Roehl, M. E., and Alvarez, P. J. J. (1996). “Chemical and microbiological assessment of pendimethalin-contaminated soil after treatment with Fenton’s reagent.” Water Res., 30(11), 2579–2586.
Miller, C. M., and Valentine, R. L. (1999). “Mechanistic studies of surface catalyzed decomposition and contaminant degradation in the presence of sand.” Water Res., 33(12), 2805–2816.
Murphy, P., Murphy, W. J., Boegli, M., Price, K., and Moody, C. D. (1989). “A Fenton-like reaction to neutralize formaldehyde waste solutions.” Environ. Sci. Technol., 23(2), 166–169.
Ogram, A. N., Jessup, R. E., Ou, L. T., and Rao, P. D. C. (1985). “Effects of sorption on biological degradation of 2,4-dechlorophenoxy acetic acid in soils.” Appl. Environ. Microbiol., 49(3), 582–587.
Pardieck, D. L., Bouwer, E. J., and Stone, A. T. (1992). “Hydrogen peroxide use to increase oxidant capacity for in situ bioremediation of contaminated soils and aquifers: A review.” J. Contam. Hydrol., 9(2), 221–242.
Pignatello, J. J., and Baehr, K. (1994). “Waste management: Ferric complexes as catalysts for “Fenton” degradation of 2,4-D and metolachlor in soil.” J. Environ. Qual., 23(2), 365–369.
Pignatello, J. J., and Day, M. (1996). “Mineralization of methyl parathion insecticide in soil by hydrogen peroxide activated with iron(III)-NTA or -HEIDA complexes.” Hazard. Waste Hazard. Mater., 13(2), 237–244.
Quan, H. N., Teel, A. L., and Watts, R. J. (2003). “Effect of contaminant hydrophobicity on dosage requirements in the Fenton-like treatment of soils.” J. Hazard. Mater., 102(2–3), 277–289.
Ravikumar, J. X., and Gurol, M. D. (1991). “Effectiveness of chemical oxidation to enhance the biodegradation of pentachlorophenol in soil: A laboratory study.” Hazardous and Industrial Wastes: Proc. of the 23rd Mid-Atlantic Industrial Waste Conf., R. D. Neufeld and L. W. Casson, eds., Technomic, Lancaster, Pa.
Ravikumar, J. X., and Gurol, M. D. (1994). “Chemical oxidation of chlorinated organics by hydrogen peroxide in the presence of sand.” Environ. Sci. Technol., 28(3), 394–400.
Sato, S., Kobayashi, T., and Sumi, Y. (1975). “Removal of sodium dodecylbenzene sulfonate with Fenton’s reagent.” Yukagaku, 24(10), 863–868.
Schmelling, D. C., Gray, K. A., and Kamat, P. V. (1998). “Radiation-induced reactions of 2,4,6-trinitrotoluene in aqueous solution.” Environ. Sci. Technol., 32(7), 971–974.
Schwarzenbach, R. P., Gschwend, P. M., and Imboden, D. M. (1993). Environmental organic chemistry, Wiley, New York.
Sedlak, D. L., and Andren, A. W. (1991). “Aqueous phase oxidation of polychlorinated biphenyls by hydroxyl radicals.” Environ. Sci. Technol., 25(9), 1419–1427.
Spain, J. C., Mulligan, J. D., Downey, D. C., and Slaughter, J. K. (1989). “Excessive bacterial decomposition of during enhanced biodegradation.” Ground Water, 27(2), 163–167.
Spencer, C. J., Stanton, P. C., and Watts, R. J. (1996). “A central composite rotatable design for the catalyzed hydrogen peroxide remediation of contaminated soils.” J. Air Waste Manage. Assoc., 88(11), 971–979.
Sudoh, M., Sasase, T., Yonebayachi, T., and Koide, K. (1985). “Oxidative degradation of aqueous phenol effluent with Fenton’s reagent.” Kagaku Kogaku Ronbunshu, 11(1), 70–76.
Sun, Y., and Pignatello, J. J. (1992). “Chemical treatment of pesticide wastes. Evaluation of Fe(III) chelates for catalytic hydrogen peroxide oxidation of 2,4-D at circumneutral pH.” J. Agric. Food Chem., 40(2), 332–337.
Teel, A. L., Warberg, C. R., Atkinson, D. A., and Watts, R. J. (2001). “Comparison of mineral and soluble iron Fenton’s catalysts for the treatment of trichloroethylene.” Water Res., 35(4), 977–984.
Teel, A. L., and Watts, R. J. (2002). “Degradation of carbon tetrachloride by Fenton’s reagent.” J. Hazard. Mater., B94(2), 179–189.
Thomas, J. M., and Ward, C. H. (1989). “In situ biorestoration of organic contaminants in the subsurface.” Environ. Sci. Technol., 23(7), 760–766.
Tyre, B. W., Watts, R. J., and Miller, G. C. (1991). “Treatment of four biorefractory contaminants in soils using catalyzed hydrogen peroxide.” J. Environ. Qual., 20(6), 832–888.
United States Department of Energy (USDOE). (1999). “Innovative technology summary report: Fenton’s reagent.” DOE/EM-0484, Office of Science and Technology, Washington, D.C.
Valentine, R. L., and Wang, D. C. A. (1998). “Iron oxide surface catalyzed oxidation of quinoline by hydrogen peroxide.” J. Environ. Eng., 124(1), 31–38.
Walling, C. (1975). “Fenton’s reagent revisited.” Acc. Chem. Res., 8(1), 125–131.
Walling, C., and Johnson, R. A. (1975). “Fenton’s reagent. V. Hydroxylation and side-chain cleavage of aromatics.” J. Am. Chem. Soc., 97(2), 363–367.
Wang, X. J., and Brusseau, M. L. (1998). “Effect of pyrophosphate on the dechlorination of tetrachloroethene by the Fenton reaction.” Envir. Toxicol. Chem., 17(9), 1689–1694.
Watts, R. J. (1992). “Hydrogen peroxide for physicochemically degrading petroleum-contaminated soils.” Remediation, 2(4), 413–425.
Watts, R. J. (1998). Hazardous wastes: Sources, pathways, receptors, Wiley, New York.
Watts, R. J., Udell, M. D., and Rauch, P. A. (1990). “Treatment of pentachlorophenol-contaminated soils using Fenton’s reagent.” Hazard. Waste Hazard. Mater., 7(4), 335–345.
Watts, R. J., Udell, M. D., and Leung, S. W. (1991). “Treatment of contaminated soils using catalyzed hydrogen peroxide.” J. A. Roth, ed., Chemical oxidation: Technology for the 90’s, Techmonic Press, 46–55.
Watts, R. J., Udell, M. D., and Monsen, R. M. (1993). “Use of iron minerals in optimizing the peroxide treatment of contaminated soils.” Period. Math. Hung., 69(12), 839–845.
Watts, R. J., Kong, S., Dippre, M., and Barnes, W. T. (1994). “Oxidation of sorbed hexachlorobenzene in soils using catalyzed hydrogen peroxide.” J. Hazard. Mater., 39(1), 33–47.
Watts, R. J., and Dilly, S. E. (1996). “Evaluation of iron catalysts for the Fenton-like remediation of diesel-contaminated soils.” J. Hazard. Mater., 51(2), 209–224.
Watts, R. J., Jones, A. P., Chen, P. H., and Kenny, A. (1997). “Mineral catalyzed Fenton-like oxidation of sorbed chlorobenzenes.” Water Resour. Res., 69(2), 269–275.
Watts, R. J., and Stanton, P. C. (1999). “Mineralization of sorbed and NAPL-phase hexadecane by catalyzed hydrogen peroxide.” Water Res., 33(6), 1405–1414.
Watts, R. J., Bottenberg, B. C., Jensen, M. E., Hess, T. H., and Teel, A. L. (1999a). “Mechanism of the enhanced treatment of chloroaliphatic compounds by Fenton-like reactions.” Environ. Sci. Technol., 33(12), 3432–3437.
Watts, R. J., Udell, M. D., Kong, S. H., and Leung, S. W. (1999b). “Fenton-like remediation catalyzed by naturally occurring iron minerals.” Environ. Eng. Sci., 16(1), 93–103.
Watts, R. J., Haller, D. R., Jones, A. P., and Teel, A. L. (2000). “A foundation for the risk-based treatment of gasoline-contaminated soils using modified Fenton’s reactions.” J. Hazard. Mater., B76(1), 73–89.
Watts, R. J., Stanton, P. C., Howsawkeng, J., and Teel, A. L. (2002). “Mineralization of a sorbed polycyclic aromatic hydrocarbon in two soils using catalyzed hydrogen peroxide.” Water Res., 36(12), 4283–4292.
Watts, R. J., Washington, D., Howsawkeng, J., Loge, F. J., and Teel, A. L. (2003). “Comparative toxicity of hydrogen peroxide, hydroxyl radicals, and superoxide anion to Escherichia coli.” Adv. Environ. Res., 7(4), 961–968.
Watts, R. J., Howsawkeng, J., and Teel, A. L. (2005). “Destruction of a carbon tetrachloride DNAPL by modified Fenton’s reagent.” J. Environ. Eng., in press.
Yeh, C. K.-J., Wu, H.-M., and Chen, T.-C. (2003). “Chemical oxidation of chlorinated nonaqueous phase liquid by hydrogen peroxide in natural sand systems.” J. Hazard. Mater., 96(1), 29–51.
Information & Authors
Information
Published In
Journal of Environmental Engineering
Volume 131 • Issue 4 • April 2005
Pages: 612 - 622
Copyright
© 2005 ASCE.
History
Received: Oct 2, 2003
Accepted: Apr 2, 2004
Published online: Apr 1, 2005
Published in print: Apr 2005
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.