Predicting Fenton-Driven Degradation Using Contaminant Analog
Publication: Journal of Environmental Engineering
Volume 126, Issue 4
Abstract
The reaction of hydrogen peroxide (H2O2) and Fe(II) (Fenton's reaction) generates hydroxyl radicals (⋅OH) that can be used to oxidize contaminants in soils and aquifers. In such environments, several factors can limit the effectiveness of chemical oxidation, including reactions involving H2O2 that do not yield ⋅OH, ⋅OH reactions with nontargeted chemicals, and insufficient iron in the soil or aquifer. Consequently, site-specific studies may be necessary to evaluate the feasibility of chemical oxidation using H2O2. Here, the degradation of a contaminant analog, α-(4-pyridyl-1-oxide) N-tert-butylnitrone (4POBN), was used to estimate ⋅OH concentration and simplify testing procedures. A kinetic model was developed, calibrated using 4POBN degradation kinetics, and used to predict the disappearance of 2-chlorophenol (2CP), a representative target. Good agreement between predicted (Y) and measured (X) values for 2CP (Y = 0.95X) suggests that the kinetics of analog degradation can be used to predict the degradation rate of compounds for which the rate constant for reaction with ⋅OH is known.
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References
1.
Boltz, D. F., and Howell, J. A., eds. (1978). Colorimetric determination of non-metals. Wiley.
2.
Buxton, G. V., Greenstock, C., Hellman, W. P., and Ross, A. B. (1988). “Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms, and hydroxyl radicals (⋅OH/⋅O−) in aqueous solution.” J. Phys. Chem. Reference Data, 17(2), 513–886.
3.
Dorfman, L. M., and Adams, G. E. (1973). “Reactivity of the hydroxyl radical.” Rep. No. NSRDS-NBS-46, Nat. Bureau of Standards, Washington, D.C.
4.
Foget, M. K. ( 1992). “Goethite-catalyzed decomposition of hydrogen peroxide formulations: Implications for in situ bioremediation,” MS thesis, Dept. of Civ. and Envir. Engrg., Washington State University, Pullman, Wash.
5.
Gethoff, N., and Solar, S. (1986). “Radiolysis and pulse radiolysis of chlorinated phenols in aqueous solutions.” Int. J. Radiation Applications and Instrumentation, Part C, Radiation, Phys. and Chem., Oxford, U.K., 28(5–6), 443–450.
6.
Haag, W. R., and Yao, C. C. D. (1992). “Rate constants for reaction of hydroxyl radicals with several drinking water contaminants.” Envir. Sci. Technol., 26(5), 1005–1013.
7.
Huling, S. G. ( 1996). “Microbial and organic matter effects on the oxidation capacity of H2O2 in soil,” PhD dissertation, Dept. of Chem. and Envir. Engrg., University of Arizona, Tucson.
8.
Huling, S. G., Arnold, R. G., Sierka, R. A., and Miller, M. R. (1998). “Measurement of hydroxyl radical activity in a soil slurry using 4POBN.” Envir. Sci. Technol., 32(21), 3436–3441.
9.
Ingles, D. L. (1972). “Oxidations studies by Fenton's reagent using redox titration.” Australian J. Chem., Melbourne, Australia, 25, 87–95.
10.
Ireland, J. C., and Valinieks, J. (1992). “Rapid measurement of aqueous hydroxyl radical concentrations in steady state HO-flux systems.” Chemosphere, 25(3), 383–396.
11.
Jayson, G. G., Parsons, B. J., and Swallow, A. J. (1973). “Some simple, highly reactive, inorganic chlorine derivatives in aqueous solution.” J. Chem. Soc. Faraday Trans. I, 69, 1597–1607.
12.
Lipczynska-Kochany, E. (1991). “Degradation of aqueous nitrophenols and nitrobenzene by means of the fenton reaction.” Chemosphere, 22(5–6), 529–536.
13.
Lipczynska-Kochany, E., Gregor, S., and Harms, S. (1995). “Influence of some groundwater and surface waters constituents on the degradation of 4-chlorophenol by the Fenton reaction.” Chemosphere, 30(1), 9–20.
14.
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. Contaminant Hydro., 9(3), 221–242.
15.
Pignatello, J. J. (1992). “Dark and photoassisted Fe3+-catalyzed degradation of chlorophenoxyl herbicides by hydrogen peroxide.” Envir. Sci. Technol., 26(5), 944–951.
16.
Ravikumar, J. X., and Gurol, M. D. (1994). “Chemical oxidation of chlorinated organics by hydrogen peroxide in the presence of sand.” Envir. Sci. Technol., 28(3), 394–400.
17.
Stokes, N. J., Tabner, B. J., and Hewitt, C. N. (1994). “The determination of hydroxyl radical concentrations in environmental chambers using electron spin resonance.” Chemosphere, 28(5), 999–1008.
18.
Tyre, B. W., Watts, R. J., and Miller, G. C. (1991). “Waste management: Treatment of four biorefractory contaminants in soils using catalyzed hydrogen peroxide.” J. Envir. Quality, (20), 832–838.
19.
Walling, C. (1975). “Fenton's reagent revisited.” Accounts of Chem. Res., (8), 125–131.
20.
Watts, R. J., Kong, S., Dippre, M., and Barnes, W. T. (1994). “Oxidation of sorbed hexochlorobenzene in soils using catalyzed hydrogen peroxide.” J. Haz. Mat., (39), 33–47.
21.
Watts, R. J., Udell, M. D., and Mosen, R. M. (1993). “Use of iron minerals in optimizing the peroxide treatment of contaminated soils.” Water Envir. Res., 65(7), 839–844.
22.
Watts, R. J., Udell, M. D., Rauch, P. A., and Leung, S. W. (1990). “Treatment of pentachlorophenol-contaminated soils using Fenton's reagent.” Haz. Waste and Haz. Mat., (7)4, 335–345.
23.
Yeh, C. K., and Novak, J. T. (1995). “The effect of hydrogen peroxide on the degradation of methyl and ethyl tert-butyl ether in soils.” Water Envir. Res., 67(5), 828–834.
24.
Zepp, R. G., Faust, B. C., and Hoigne, J. (1992). “Hydroxyl radical formation in aqueous reactions (pH3-8) of iron(II) with hydrogen peroxide: The photo-Fenton reaction.” Envir. Sci. Technol., 26(2), 313–319.
Information & Authors
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Published In
Journal of Environmental Engineering
Volume 126 • Issue 4 • April 2000
Pages: 348 - 353
History
Received: Aug 4, 1998
Published online: Apr 1, 2000
Published in print: Apr 2000
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