Numerical Simulation of Bromate Formation during Ozonation of Bromide
Publication: Journal of Environmental Engineering
Volume 129, Issue 11
Abstract
The purpose of this study is to develop a kinetic model that links decomposition reactions from the TFG ozone decay model with recognized oxidation reactions, secondary •OH reactions, and reactions in order to improve decay and bromate formation prediction capabilities under multiple water quality conditions. The model was compared with experimentally measured ozone decomposition and final bromate concentration data sets provided by two researchers. The data sets included varying pH (6.5–8.5), initial hydrogen peroxide (0–1 mM), and initial bromide concentration (0.1–1 mM). Model verification was carried out by sensitivity analysis of the rate constants and then optimization of the most sensitive rate constants using the method of least squares. Model predicted ozone decay data was analyzed and compared with measured ozone decay data using R-squared statistic for linear regression model. The model predicted final bromate concentration is analyzed by comparing it with the residual Δ(%) between experimental and model results. The TFG model was effectively tested for multiple data sets and it was found that model prediction was a success both for ozone decay (regression coefficients >0.95 for all experimental conditions but one) and bromate prediction with residual of less than 100% for all experimental conditions except low peroxide dose (<20 μm).
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References
Beck, G.(1969). “Detection of charged intermediate of pulse radiolysis by electrical conductivity measurements.” Int. J. Radiat. Phys. Chem., 1(3), 361–371.
Bielski, H. J., Benon, H. J., Cabelli, D. E., Ravindra, L. A., and Alberta, A. B.(1985). “Reactivity of perhydroxyl/superoxide radicals in aqueous solution.” J. Phys. Chem. Ref. Data, 14(4), 1041–1100.
Bühler, R. E., Staehelin, J., and Hoigné, J.(1984). “Ozone decomposition in water studied by pulse radiolysis. 1. and as intermediates.” J. Phys. Chem., 88, 2560–2564.
Buxton, G. V., and Dainton, F. S.(1968). “The radiolysis of aqueous solutions of oxybromine compounds; the spectra and reactions of BrO and ” Proc. R. Soc. London, Ser. A, 304, 427–439.
Buxton, G. V., Greenstock, C. L., Helman, W. P., and Ross, A. B.(1988). “Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals in aqueous solution.” J. Phys. Chem. Ref. Data, 17(2), 513–886.
Chelkowska, K., Grasso, D., Fábián, I., and Gordon, G.(1992). “Numerical simulations of aqueous ozone decomposition.” Ozone: Sci. Eng., 14(1), 33–49.
Deshpande, M. (2000). “Numerical simulation of aqueous ozone decay and bromate formation during ozonation of bromide-containing waters.” Master thesis, Univ. of Akron, Akron, Ohio.
Federal Register. (1994). 59(No. 145), 38668.
Field, R. J., Raghavan, N. V., and Brunner, J.(1982). “A pulse radiolysis investigation of the reaction of bromine dioxide radical with hexacyanoferrate (II), phenoxide ion, and phenol.” J. Phys. Chem., 86, 2443–2449.
Glaze, W. H., and Kang, J. W.(1998). “Advanced oxidation processes for treating groundwater contaminated with TCE and PCE: laboratory studies.” J. Am. Water Works Assoc., 80(5), 57–63.
Gordon, G.(1995). “The chemical aspects of bromate control in ozonated drinking water containing bromide ion.” Water Supply,13, 35–43.
Gyürék, L. L., Li, H., Belsovic, M., and Finch, G. F.(1999). “Ozone inactivation kinetics of Cryptosporidium in phosphate buffer.” J. Environ. Eng., 125(10), 913–924.
Haag, W. R., and Hoigné, J.(1983). “Ozonation of bromide-containing drinking waters: kinetics of formation of hypobromous acid and bromate.” Environ. Sci. Technol., 17, 261–267.
Haag, W. R., Hoigné, J., and Bader, H.(1982). “Ozonation of bromide-containing drinking waters: formation kinetics of secondary bromine compounds.” Vom Wasser,59, 237–251.
Kläning, U. K., and Wolff, T.(1985). Ber. Bunsenges. Phys. Chem., 89, 243–245.
Koppenol, W. H., Butler, J., and Leeuwan, J. W. L. V.(1978). “The Haber-Weiss cycle.” Photochem. Photobiol., 28, 655–660.
Mamou, A., Rabani, J., and Behar, D.(1977). “Oxidation of aqueous bromide by hydroxyl radicals, studies by pulse radiolysis.” J. Phys. Chem., 81(15), 1447–1478.
Maruthamuthu, P., and Neta, P.(1978). “Phosphate radicals. Spectra, acid-base equilibria, and reactions with inorganic compounds.” J. Phys. Chem., 82, 710–713.
Nemes, A., Fábián, I., and Gordon, G.(2000). “Experimental aspects of mechanistic studies on aqueous ozone decomposition in alkaline solution.” Ozone: Sci. Eng., 22(3), 287–304.
Ozekin, K., Westerhoff, P., Amy, G. L., and Siddiqui, M.(1998). “Evaluating molecular ozone and radical pathways of bromate formation during ozonation.” J. Environ. Eng., 124(5), 456–462.
Richardson, S. D., Caughran, T. V., Poiger, T., Guo, Y., and Crumley, F. G. (2000). “Identification of polar drinking water disinfection by-products using liquid chromatography-mass spectrometry.” Natural organic matters and disinfection by-products, S. E. Barrett, S. E. Krasner, and G. L. Amy, eds., American Chemical Society, Washington D.C., 374–388.
Schested, K., Rasmussen, O. L., and Fricke, H.(1968). “Rate constant of •OH with and from hydrogen peroxide formation in pulse-irradiated oxygenated water.” J. Phys. Chem., 72, 626–631.
Schwarz, H. A., and Bielski, B. H.(1986). “Reactions of and with iodine and bromine and the and I atom reduction potentials.” J. Phys. Chem., 90, 1445–1448.
Siddiqui, M. S., and Amy, G. L.(1993). “Factors affecting DBP formation during ozone-bromide reactions.” J. Am. Water Works Assoc., 85(1), 63–72.
Sidgwick, N. V. (1952). The chemical elements and their compounds, Oxford University Press, Oxford, U.K.
Singer, P. C. (1999). Formation and control of disinfection by-products in drinking water, American Water Works Association, Denver.
Snoeyink, V. L., and Jenkins, D. (1980). Water chemistry, Wiley, New York.
Song, R. (1996). “Ozone-bromide-NOM interactions in water treatment.” PhD dissertation, Univ. of Illinois, Urbana-Champaign, Ill.
Song, R., Westerhoff, P., Minear, R., and Amy, G. L.(1997). “Bromate minimization during ozonation.” J. Am. Water Works Assoc., 89(6), 69–78.
Staehelin, J., Bühler, R. E., and Hoigné, J.(1984). “Ozone decomposition in water studied by pulse radiolysis. 2. OH and as chain intermediates.” J. Phys. Chem., 88, 5999–6004.
Staehelin, J., and Hoigné, J.(1982). “Decomposition in water: rate of initiation by hydroxide ions and hydrogen peroxide.” Environ. Sci. Technol., 16, 676–681.
Sutton, H. C., Adams, G. E., Boag, J. W., and Michael, B. D. (1965). Pulse radiolysis, M. Ebert, J. P. Keene, A. J. Swallow, and J. H. Baxendale, eds., Academic, London, 61–81.
Sweetman, J., and Simmons, M.(1980). “The production of bromophenols resulting from the chlorination of waters containing bromide ion and phenol.” Water Res., 14, 287–290.
Taub, H., and Bray, W. C.(1940). “Chain reactions in aqueous solutions containing ozone, hydrogen peroxide and acid.” J. Am. Water Works Assoc., 62, 3357–3373.
Tomiyasu, H., Fukutomi, H., and Gordon, G.(1985). “Kinetics and mechanism of ozone decomposition in basic aqueous solution.” Inorg. Chem., 24, 2962–2966.
Von Gunten, U., and Hoigné, J.(1994). “Bromate formation during ozonation of bromide-containing waters: interaction of ozone and hydroxyl radical reactions.” Environ. Sci. Technol., 28, 1234–1242.
Von Gunten, U., and Oliveras, Y.(1997). “Kinetics of the reaction between hydrogen peroxide and hypobromous acid: implication on water treatment and natural systems.” Water Res., 4, 900–906.
Von Gunten, U., and Oliveras, Y.(1998). “Advanced oxidation of bromide-containing waters: bromate formation mechanisms.” Environ. Sci. Technol., 32, 63–70.
Weinstein, J., Benon, H. J., and Bielski, H. J.(1979). “Kinetics of the interaction of and radicals with hydrogen peroxide.” J. Am. Chem. Soc., 101, 58–62.
Westerhoff, P. (1995). “Ozone oxidation of bromide and natural organic matter.” PhD dissertation, Univ. of Colorado, Boulder, Colo.
Westerhoff, P., Song, R., and Minear, R.(1998). “Numerical kinetic models for bromide oxidation to bromine and bromate.” Water Res., 32, 1687–1699.
Yates, R. S., and Stenstrom, M. K. (1993). “Bromate production ozone contactors.” AWWA Annual Conf. Proc., San Antonio.
Zehavi, D., and Rabani, J.(1972). “Oxidation of aqueous bromide ions by hydroxyl radicals. Pulse radiolytic investigation.” J. Phys. Chem., 76(3), 312–319.
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Published In
Journal of Environmental Engineering
Volume 129 • Issue 11 • November 2003
Pages: 991 - 998
Copyright
Copyright © 2003 American Society of Civil Engineers.
History
Received: Jan 15, 2002
Accepted: Dec 16, 2002
Published online: Oct 15, 2003
Published in print: Nov 2003
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