Ozonation of bromide-containing waters:  kinetics of formation of hypobromous acid and bromate

Haag, Werner R.; Hoigne, Juerg.

doi:10.1021/es00111a004

Cited by 493 publications

(255 citation statements)

References 22 publications

(41 reference statements)

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“…Bromide was assumed to be directly oxidized to bromate, although in reality ozone first oxidizes bromide to form hypobromous acid and hypobromite. The latter is further oxidized to bromite which finally forms bromate [23,26,27]. As such, one rate constant for bromate formation was determined after calibration and the stoichiometric coefficients from this process were derived from a reaction where 1 mole of bromate is formed out of 1 mole of both ozone and bromide.…”

Section: 3modelling Approachmentioning

confidence: 99%

Full-scale modelling of an ozone reactor for drinking water treatment

Audenaert

Callewaert

Cromphout³

et al. 2010

Chemical Engineering Journal

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In 2003, the Flemish Water Supply Company (VMW) extended its drinking water production site in Kluizen (near Ghent, Belgium) with a combined ozonation and biological granular activated carbon filtration (BGAC) process. Due to this upgrade, biostability increased, less chlorination was needed and drinking water quality improved significantly. The aim of this study was to describe the full-scale reactor with a limited set of equations. In order to describe the ozonation process, a model including key processes such as ozone decomposition, organic carbon removal, disinfection and bromate formation was developed. Kinetics were implemented in WEST ® and simulation results were compared to real data. The predicting performance was verified with a goodness of fit test and key parameters were determined through a local sensitivity analysis. Parameters involving optical density (both rate constants and stoichiometric coefficients) strongly affect model output Some parameters with respect to bromate and bacteria showed to be only, but to a large extent, sensitive to their associated concentrations. A scenario analysis was performed to study the system's behavior at different operational conditions. It was demonstrated that the model is able to describe the operation of the full-scale ozone reactor, however, further data collection for model validation is necessary.

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Section: 3modelling Approachmentioning

confidence: 99%

Full-scale modelling of an ozone reactor for drinking water treatment

Audenaert

Callewaert

Cromphout³

et al. 2010

Chemical Engineering Journal

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“…b The Henry's Law constant is from Schweitzer et al (2000); The value in parentheses is the effective Henry's law constant K * H at pH 5 accounting for (Arnaud, 1966). c HOBr(aq)/BrO − acid dissociation is negligible under atmospheric conditions (K a = 1.6 × 10 −9 M, Haag and Hoigne, 1983). d McGrath and Rowland (1994) e Br 2 (aq) dissociation by hydrolysis can be neglected (Beckwith et al, 1996).…”

mentioning

confidence: 99%

Tropospheric bromine chemistry: implications for present and pre-industrial ozone and mercury

et al. 2012

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Abstract. We present a new model for the global tropospheric chemistry of inorganic bromine (Br y ) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Br y include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by < 1-8 nmol mol −1 (6.5 % globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4 %. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40 % higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

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“…These DBPs are also 53 fully or partly regulated in drinking water in other countries (e.g., European Union 13 , China 14 ). 54 Unlike ozone which can further oxidize HOBr to potentially toxic bromate (BrO 3 − ), [15][16][17] the 55 rate constant for the reaction between HOCl and HOBr is low. 18 Therefore, BrO 3 − formation 56 from chlorination of bromide-containing waters in water treatment is generally insignificant.…”

mentioning

confidence: 99%

Formation of Bromate and Halogenated Disinfection Byproducts during Chlorination of Bromide-Containing Waters in the Presence of Dissolved Organic Matter and CuO

Liu

Croué

2015

Environ. Sci. Technol.

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Previous studies showed that significant bromate (BrO 3 − ) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the formation of BrO 3 − and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO 3 − formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di-and tricarboxylic acids (oxalic, malonic, succinic, and citric acids), BrO 3 − formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0−0.2 g L −1 ) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO 3 − , total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems.

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Ozonation of bromide-containing waters: kinetics of formation of hypobromous acid and bromate

Abstract: Ozone oxidizes Br" under water treatment conditions to form HOBr. HOBr reacts further with 03, but only in c

Cited by 493 publications

References 22 publications

Full-scale modelling of an ozone reactor for drinking water treatment

Full-scale modelling of an ozone reactor for drinking water treatment

Tropospheric bromine chemistry: implications for present and pre-industrial ozone and mercury

Formation of Bromate and Halogenated Disinfection Byproducts during Chlorination of Bromide-Containing Waters in the Presence of Dissolved Organic Matter and CuO

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