A Simple Model to Predict Formation of Bromate Ion and Hypobromous Acid/Hypobromite Ion through Hydroxyl Radical Pathway during Ozonation

A simple model is developed to predict the formation of bromate ion as well as hypobromous acid/hypobromite ion through the hydroxyl radical pathway. For simplicity of the model, hydroxyl radical concentrations are represented by the concentration ratio of hydroxyl radical to dissolved ozone under the different pH conditions. A kinetic analysis is conducted to evaluate the ratio under the different pH conditions based on the experimental data. The different extent of the ratio by one pH unit is found to be 3–4 times. This model can favorably simulate the formations of bromate ion as well as hypobromous acid/hypobromite ion in spite of the simplicity of the model. So it is likely that this model will be applicable to the prediction of bromate ion formation in water purification process such as drinking water treatment by introducing the concentration ratio of hydroxyl radical to dissolved ozone.     

Modification of the Standard Neutral Ozone Decomposition Model

The modified Staehelin, Buhler, and Hoigné model for aqueous ozone decomposition was tested over a wide range of hydroxyl radical scavenger concentrations at a pH of 7.1–7.2. Results from these experiments showed that the modified model appeared to underpredict the residual ozone concentration and overpredict the residual hydroxyl radical probe compound, tetrachloroethylene, concentration. The modified Staehelin, Buhler, and Hoigné model was recalibrated and two rate constants, the rate constant of the initiation reaction of ozone decomposition of hydroxide ion and the rate constant of the promotion reaction of ozone decomposition by hydroxyl radical, were reestimated. The new estimates of these rate constants are 1.8 × 10² M^?1s^?1 (initiation reaction) and 2 × 10⁸ M^?1s^?1 (promotion reaction), while the values estimated by Staehelin, Buhler, and Hoigné for these rate constants are 70 M^?1s^?1 (initiation reaction) and 2 × 10⁹ M^?1s^?1 (promotion reaction). The recalibrated-modified model was tested and validated by conducting experiments at different pH values and hydroxyl radical scavenger concentrations. Also, the effect of phosphate buffer as a hydroxyl radical scavenger was investigated at phosphate buffer concentrations of 10 mM and 1 mM.     

Parameters Affecting the Formation of Bromate Ion During Ozonation

Batch type ozone experiments conducted on aquatic humic substances solutions spiked with bromide ion were developed to evaluate the importance of various parameters that may affect the formation of bromate ion during ozonation. The nature of the NOM, the alkalinity, the bromide ion content and the presence of ammonia were found to significantly affect the bromate ion production. Temperature and pH can be considered as minor factors. The ozonation of a clarified surface water using a continuous flow ozone contactor have shown that the addition of a low quantity of ammonia (0.05 to 0.1 mg/L NNH₄ ⁺) appeared to be an interesting option for controlling the bromate formation. On the contrary, the addition of hydrogen peroxide may enhance or reduce the bromate ion production, depending on the applied hydrogen peroxide/ozone ratio.     

Obtaining Real-Time Kinetic Parameters on Ozone Decay from a Full-Scale Ozone Contactor Using the Axial Dispersion Reactor Model

Ozone decay kinetic parameters, including fast ozone demand ([D]₀), ozone decay rate constant (k_D), and rate constant for ozone reaction with ozone demand (k_R), are required for a numerical simulation targeting the design and operational optimization of an ozone contactor. The kinetic parameters of ozone decay and dispersion number were obtained from a full-scale ozone contactor for the axial dispersion reactor model simulation. The sensitivity analysis showed that the influence of k_R was minor and the constant 13 L mg^?1 min^?1 for k_R was suitable for carrying out simulations for sand-filtered raw water without measuring it. Curve fitting with on-site ozone concentrations and the ADR simulation results using a trial-and-error method could successfully provide kinetic parameters on ozone decay (i.e., k_D and [D]₀). Using these real-time kinetic parameters, we successfully predicted the CT, residual ozone, C. parvum log inactivation, and bromate formation. Compared to a method based on the CSTR in series, this method could provide more accurate CT and residual ozone for an ozone contactor with horizontal meandering flow and low dispersion number.     

Compromise Between Bromate Ion Formation and Pesticides Degradation and/or Manganese Removal

Ozonation is a widely used technology within the water industry. Bromate ion formed by oxidation of water containing bromide ion was studied with the Gas Ozone Test and Pilot Scale Ozonation. Bromate ion formation was investigated along with the removal of triazines and/or manganese. Under identical conditions of ozonation, BrO₃ ^? formation is specific for each water and depends on parameters such as Total Organic Carbon, UV absorbance at 254 nm, applied ozone and ozone residual. Pesticides degradation by ozonation alone cannot be achieved without the formation of BrO₃ ^? at a high concentration. Hydrogen peroxide, at a constant ozone dose, reduces the BrO₃ ^? formation. However, even with the use of hydrogen peroxide, the concentration of BrO₃ ^? can remain in excess of the provisional Maximum Contaminant Level (10 μg/L). For certain types of water, pesticide degradation is difficult to achieve if the MCL for BrO₃ ^? has to be met. Manganese oxidation by ozone appears to be achieved without high bromate formation; indeed the presence of manganese hinders BrO₃ ^? formation.     

Kinetic Study of Ozone Decay in Homogeneous Phosphate-Buffered Medium

The ozone decomposition reaction is analyzed in a homogeneous reactor through in-situ measurement of the ozone depletion. The experiments were carried out at pHs between 1 to 11 in H₂PO₄^?/HPO₄^2– buffers at constant ionic strength (0.1 M) and between 5 and 35 °C. A kinetic model for ozone decomposition is proposed considering the existence of two chemical subsystems, one accounting for direct ozone decomposition leading to hydrogen peroxide and the second one accounting for the reaction between the hydrogen peroxide with the ozone to give different radical species. The model explains the apparent reaction order respect of the ozone for the entire pH interval. The decomposition kinetics at pH 4.5, 6.1, and 9.0 is analyzed at different ionic strength and the results suggest that the phosphate ions do not act as a hydroxyl radical scavenger in the ozone decomposition mechanism.     

Ozonation of Polycyclic Aromatic Hydrocarbons in Water Solution

The degradation of three polycyclic aromatic hydrocarbons (PAHs): benzo[a]pyrene (BAP), chrysene (CHR), and fluorene (FLU) in aqueous solution using ozone was investigated. The influence of pH of the reaction mixture, ozone concentration, and the presence of a radical scavenger on the reaction rate was determined. The highest rate of PAHs disappearance was achieved in acidic solutions. The radical scavenger, tert-butanol, effectively inhibited the rate of PAHs destruction. The rate constants of direct reaction of PAHs with ozone were calculated and they were equal to (3.32 ± 0.21) × 10⁴; (1.10 ± 0.15) × 10⁴ and 44.8 ± 1.1 M^?1s^?1 for BAP, CHR, and FLU, respectively. The contributions of direct ozonolysis, and radical reaction to PAHs oxidation in ozonation processes, were evaluated.     

Bromate Formation in Ozone and Advanced Oxidation Processes

Both the direct ozone reaction and the indirect hydroxyl radical reaction are important in ozonation of drinking water. This article investigates the effectiveness of ozone versus the advanced oxidation process of ozone coupled with hydrogen peroxide in the formation of bromate. The investigation was conducted on a pilot scale at various H₂O₂:O₃ dose ratios of 0.1, 0.2, and 0.35 at different times of the year. The results of this study show a reduction in bromate with the addition of hydrogen peroxide to an ozone system versus ozone alone. It was also observed that bromate increased with increased H₂O₂:O₃ ratios; however, concentrations were still lower than those in the ozone only system.     

Chemical degradation of aldicarb in water using ozone

The use of ozone to degrade aldicarb in water was investigated under different conditions. The oxidation develops through the direct attack of ozone since the presence of hydroxyl radical inhibitors, such as tert-butanol, does not affect the degradation rate of aldicarb. The combination of ozone with hydrogen peroxide does not improve the oxidation rate which also confirms the absence of radical reactions to eliminate aldicarb. However, TOC removal increases 51% in the presence of hydrogen peroxide after 65 min of oxidation. The oxidation rate is strongly affected by the type of device for feeding ozone, which indicates that a fast gas-liquid reaction is taking place. Therefore, mass transfer and chemical reaction steps are important factors in the establishment of the global rate of oxidation. Application of kinetic equations derived from gas absorption theories allows the determination of the rate constant of the direct ozone–aldicarb reaction, which was found to be: k = 3·18 × 10¹¹ exp(–6000/T) m³ mol^?1s^?1.     

Impact of Water Temperature on Resolving the Challenge of Assuring Disinfection While Limiting Bromate Formation

Intensive pilot studies were performed to study the impact of ozone dose (0.6 to 3.5 mg/L), pH (6.0 to 7.5), and contact time (12 to 38 min) on bromate (BrO₃) formation, for different sand-filtered water qualities from the Neuilly-sur-Marne Treatment Plant (COT = 1.3 to 2.2 mg/L, TAC = 190 to 230 mg CaCO₃, [Br^?] = 25 to 50 μg/L, and T = 5°C to 26°C). Whatever the water quality studied, the main factors influencing bromate formation were ozone dose, pH, and a cross factor between them. Bromate formation was shown to be proportional to bromide concentration, and to increase only slightly with temperature, depending on the ozone dose and the pH. As on the contrary temperature has an important impact on disinfection, especially when considering Cryptosporidium inactivation, resolving the challenge of ensuring disinfection while limiting bromate formation was shown to be quite easily achievable, at intermediate temperature, and with more stringent conditions at high temperature (because of bromate formation) or at low temperature (because of disinfection).     

Results Of Bromide And Bromate Monitoring At Several Water Treatment Plants

The ozonation of water is a widely used technology within the water industry. Recent toxicological studies have shown that high bromate ion intake induces a high incidence of tumors in rats. Bromate ion formation from oxidation of water containing bromide ion was examined at nine treatment plants and one pilot. We found bromate ion (> 2 μg/L) in drinking water containing bromide ion when treated with ozone at pH greater than 7.0, even in the presence of ammonia. Bromate ion formation increased with the applied ozone dose. But bromate ion must be considered also as a byproduct of commercial sodium hypochlorite solutions. Under commercial conditions, chlorine dioxide and granular activated carbon had no effects on bromate levels.     

Characterization of Natural Water for Potential to Oxidize Organic Pollutants with Ozone

A laboratory study has been designed to investigate the decomposition of ozone in natural water and to determine its potential to produce hydroxyl free radicals for the oxidation of micropollutants during the ozonation process of drinking water. This report describes the first data obtained using a continuous flow reactor capable of observing reactions with relatively short time scales (Q = 34 mL/min; 1.4 < t_c < 27 sec). Rates of ozone decay were studied in fulvic acid solution in the presence, or in the absence of radical scavenger (tert-butyl alcohol) or of promoter of ozone decomposition (formic acid), and a micropollutant of interest (tetrachloroethylene). Also, three natural waters were studied, illustrating that OH radical formation depends on chemical composition of the waters.     

Kinetics of MIB and Geosmin Oxidation during Ozonation

Ozonation is an effective means for oxidation of two common earthy/musty odorants (MIB and geosmin) in drinking waters. Second order constants were experimentally determined between the two odorants with ozone and hydroxyl radicals (HO^?). Geosmin was oxidized faster than MIB. Under most surface water treatment conditions, hydroxyl radical mediated reactions dominate over ozone reactions during MIB or geosmin oxidation. MIB and geosmin oxidation increases with greater ozone dose, higher pH, higher temperature or addition of H₂O₂.     

Bicarbonate Effect in the Ozone-UV Process in the Presence of Nitrate

Ozonation and advanced oxidation processes (AOP) are very efficient methods for the destruction of refractory organic matters. These virtues have always been related to the production of hydroxyl radicals HO^?, which are extremely powerful and non-selective oxidants. In this study, the O₃-UV process is used as an AOP, where hydroxyl radicals are generated from the photodecomposition of ozone by short wavelength ultraviolet radiation. The obtained results indicated a weak scavenging effect of tert-butanol proving that hydroxyl radicals and ozone are not the only oxidants existing in the medium. Moreover, bicarbonate, known for a long time as effective HO^? radical scavengers, does not slow down the oxidation of benzoic acid, but surprisingly increases it. Chlorides significantly decrease the degradation of organic compounds through their reaction with HO^? radicals to produce chlorine. Carbonate radicals, nitrate and nitrogenated species as peroxynitrite/?peroxynitrous acid are involved in the oxidative mechanisms.     

Investigation on the Kinetics of Heterogeneous Catalytic Ozone Decomposition in Aqueous Solution over Composite Iron-Manganese Silicate Oxide

The kinetics of heterogeneous catalytic ozone decomposition in aqueous solution over composite iron-manganese silicate oxide (FMSO) was investigated. Results showed that the presence of FMSO significantly accelerated the ozone decomposition rate from 0.022 (without FMSO) to 0.101 min^?1. The effects of inorganic anions and solution pH indicated that surface hydroxyl groups on FMSO were the active sites for catalyzing ozone decomposition and neutral charge surface seemed to show the highest catalytic performance. Tert-butanol inhibition experiments demonstrated that FMSO effectively accelerated the transformation rate of ozone into hydroxyl radicals. The contribution of hydroxyl radicals on ozone decomposition with and without FMSO was subsequently determined.     

Effect of pH and Importance of Ozone initiated Radical Reactions In Inactivating Bacillus subtilis Spore

The effect of pH on the inactivation of Bacillus subtilis spores with ozone in a batch reactor was examined in association with the role of OH radicals. The exact effect OH radicals have on ozone inactivation of microorganism is not well understood, although a direct reaction of molecular ozone has sometimes been emphasized. This study reports a novel observation that the presence of OH radicals plays a significant role in microbial inactivation. Considering the dependence of the ozone decay rate on pH, the observed C¯ T values for achieving a 2 log inactivation using the modified Chick-Watson model was 40 % lower at pH 8.2 compared to that at pH 5.6. In the presence of OH radical scavengers (tert-butanol), the observed change of C¯ T with pH was within 10%. This difference could be explained by the significant role of OH radicals.     

Modeling of Ozonation for Dissolved Ozone Dosing

Experimental research was carried out for calibration and validation of a model describing ozone decay and ozone exposure (CT), decrease in UV absorbance at 254 nm (UVA₂₅₄), increase in assimilable organic carbon concentration and bromate formation. The model proved to be able to predict these parameters on the basis of the applied ozone dosage. The experimental ozone dosages ranged from 0.4 mg-O₃/L to 0.9 mg-O₃/L for natural water with a dissolved organic carbon concentration of 2.4 mg-C/L. The UVA₂₅₄ was found to be an effective parameter for estimation of rapid ozone decay for natural water under experimental conditions tested. The experimental setup consisted of a bench-scale plug flow reactor (approximately 100 L/h) with dissolved ozone dosing.     

Effect of Addition of Ammonia on theBromate Formation During Ozonation

Continuous ozonation experiments of bromide solutions have been conducted in the presence of ammonia. Solutions were prepared with phosphate-buffered NOM-free water (pH = 8) spiked with high levels of bromide and ammonium ions according variable molar ratio R= NH₄ ⁺/Br^?. Our results have shown that in the presence of tertbutanol, the bromate formation presents a delay increasing with the value of R. Bromate formation occurs when total bromine measured by the DPD colorimetric method presents a minimum level and when total bromine measured by the DPD + KI colorimetric method reaches a maximum level. The hypothesis that dibromamine was not quantitatively measured by DPD alone was first made, but unconfirmed, by complementary experiments. So we assumed that, in our experimental conditions, an unknown by-product measured by DPD + KI could be formed by ozonation of bromide in the presence of ammonia. The nitrate formation was found to be lower than expected, probably due to autonomous bromamine decomposition into nitrogen.