Bromate in Drinking Water A problem in Switzerland?

Ozonation of bromide-containing waters causes the formation of bromate which is considered to be potentially carcinogenic. An investigation in Switzerland on water works using ozone (85) has shown that the new drinking water standard of 10?µg/L for bromate is generally not exceeded. This is mainly due to the relatively small bromide concentrations which are typically below 25?µg/L. There is a characteristic relationship between bromate formation and the ozone exposure in a particular water type. This can be used to estimate the integral ozone exposure from the bromate formation which allows the assessment of the efficiency of the disinfection. This new concept is illustrated by means of two examples.     

A Survey of Bromate Ion in European Drinking Water

A one-year programme of research on the formation of bromate ion and organobrominated compounds by water ozonation was initiated recently between four French water treatment companies (C.G. Eaux, Lyonnaise des Eaux-Dumez, SAUR and SAGEP), one Spanish company (SGAB), the IARC, the KIWA, the WRc and the University of Poitiers. The programme comprises five aspects. The objective of this paper is to present the entirety of data from the following aspects: (I) inventory of the bromate ion content in distributed drinking water, and (ii) study of the evolution of bromate ion during the water treatment process.     

The Influence of the Removal of Specific NOM Compounds by Anion Exchange on Ozone Demand,Disinfection Capacity,and Bromate Formation

This research on a pilot scale focuses on the reaction of ozone with natural organic matter (NOM) for three water qualities with different dissolved organic carbon (DOC) concentrations and NOM compositions, obtained after several stages of an anion exchange process. It was shown that for the same ozone dosage per DOC, the ozone demand was higher, less bromate was formed and a lower disinfection capacity was reached for water containing mainly humic substances, than for water where the humic substances were partly removed. It can be concluded that NOM composition, specifically the humic substances, influences the ozone demand, disinfection capacity and bromate formation.     

Bromate Control by Dosing Hydrogen Peroxide and Ammonia during Ozonation of the Yellow River Water

Ozonation of the downstream Yellow River water yields bromate with concentrations higher than China regulations. Bench tests demonstrated that dosing ammonia or hydrogen peroxide alone could not control the bromate concentration to below 10 μg/L. A pilot study showed that dosing hydrogen peroxide into the inherently ammonia-containing raw water at a dosage lower than 1.7 could effectively reduce the bromate concentration to below the detection limit when the ozone dosage was between 2 and 2.5 mg/L.     

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.     

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.     

Prediction of Bromate Formation Using Multi-Linear Regression and Artificial Neural Networks

The main objective of this study was to develop simple models for the prediction of bromate formation in ozonated bottled waters, using rapidly and practically measurable raw water quality and/or operational parameters. A total of 6 multi-linear regression (MLR) with or without principal component analysis (PCA) and 2 artificial neural networks (ANN) models with multilayer perceptron architecture were developed for the prediction of bromate formation. PCA was employed to better identify relations between variables and reduce the number of variables. Experimental data used in modeling was provided from the ozonation of samples from 5 groundwater sources at various applied ozone dose and contact time. MLR models#1 and #2 well-predicted bromate formation although correlations (i.e., the signs of regression constants) among pH (as input variable) and bromate concentrations did not agree with the chemistry. MLR model#6, containing practical input parameters that are measured on-line in full-scale treatment plants, adequately predicted bromate formation and agreed with the chemistry, although fewer input parameters were used compared to MLR#1 and #2. Although both of the ANN models exhibited high regression coefficients (R²) (0.97 for both) ANN#1 was found to provide better prediction of bromate formation based on mean square error (MSE) values. However, since ANN#2 included easily measurable input parameters it may be practically used by water companies employing ozonation. Results overall indicated that ANN models have stronger prediction capabilities of bromate formation than MLR models. ANN modeling appears to be a strong tool in situations where the relations between variables are non-linear, interactive and complex, as in the bromate formation by ozonation.     

Threshold Levels for Bromate Formation In Drinking Water

Ozone is a sufficiently strong oxidant to cause the oxidation of bromide ion and formation of bromate ion. In this study, bromate ion formation in a wide variety of drinking water sources was analyzed, with bromate ion formed in all sources under drinking water treatment conditions. Threshold levels for pH, bromide ion concentration, and ozone dose were found to be source-specific. Two non-linear empirical models were developed to predict bromate ion formation; these models are easy to use and require only several water quality and treatment variables. The models were tested against several literature data and a good simulation was found in other bench-scale tests, whereas the model tended to under-predict bromate ion formation in pilot-scale and full-scale programs.     

Bromate Formation during Ozonation of Bromide Containing Drinking Water- a Pilot Scale Study

The effect of bromide ion concentration, pH, temperature, alkalinity, and hydrogen peroxide content on bromate formation was studied. Increase in pH was found to give the greatest increase in bromate formation. Also increase in the ozonation temperature, bromide ion concentration and hydrogen peroxide content increased the observed bromate concentration. Only increased alkalinity decreased the bromate formation during the ozonation experiments. Bromate formation exceeded the EU limit value for bromate ion, 10 μg/l, when the initial bromide ion concentration was around 100 μg/l, except for the alkalinity of 1.4 mmol/1, when the bromate formation was 9.4 μg/l.     

Comparative Assessment of Bromate Control Options

Various bromate control options were assessed through an intensive pilot testing program, performed with a four-cell bubble contactor, and focused on intermediate ozonation of conventionally-treated sand-filtered water. Both acid addition and ammonia addition independently provided good bromate reduction, with their combinational addition providing no further reduction. On a CT basis, the use of a static mixer did not increase bromate formation, while staged ozonation enhanced bromate formation over single stage application.     

Bromate Surveys in French Drinking Waterworks

Two bromate surveys were made recently in order to evaluate the frequency of bromate appearance in drinking waters issued from waterworks including one or two ozonation steps. The First survey was carried out on 47 waterworks. Two sampling campaigns were analyzed in cool and warm seasons. The objective of the second survey was to follow, during 4 to 10 months, at 12 selected waterworks.

The aim of this paper is to present the data obtained and to try to model for some waterworks the bromate formation by means of some important parameters (Br, O₃/DOC, T° and pH) of water to ozonate.

The main conclusion is that the bromate presence in distributed drinking waters is a reality for waterworks using ozonation steps, especially in warm period of the year. In the case of some waterworks, disinfection by sodium hypochlorite increased bromate levels in distributed water.

As shown by others on a laboratory-scale level, a multi-linear regression allows us the prediction of the bromate formation from some determining parameters, for some waterworks. However, the poor values of the linear regression lead us to have some doubts about its universal application in the real situation of an operating waterworks. A better evaluation of “C.t” will be required in the future in order to get a better prediction by the use of multi linear regression.     

Pilot-Scale and Full-Scale Evaluation of the Chlorine-Ammonia Process for Bromate Control During Ozonation

An innovative approach to minimize bromate formation using sequential chlorine and ammonia (Cl₂-NH₃ process) was developed at pilot scale and validated in a full-scale drinking water facility. Pilot-scale results showed the Cl₂-NH₃ process minimized bromate formation by 65–95% compared to 40–70% using ammonia only. A 90-day full-scale evaluation confirmed the Cl₂-NH₃ process could prevent bromate concentrations from exceeding 10 μg/L. Full-scale implementation of the Cl₂-NH₃ process allowed an increase in ozone exposure level from 3.0 mg-min/L to 8.6 mg-min/L at 15.1°C. The increased exposure level is important as drinking water utilities strive to meet more stringent drinking water regulations such as Cryptosporidium inactivation.     

Inhibition of Nano-Metal Oxides on Bromate Formation during Ozonation Process

Simulation studies in pure water were conducted to investigate the effect of nano-metal oxides on bromate (BrO₃^?) formation as catalysts and the catalytic mechanism. Results indicated that compared to ozonation alone, both nano-SnO₂ and nano-TiO₂ could inhibit the formation of bromate during ozonation process. The inhibition efficiency of BrO₃^? formation by nano-TiO₂ enhanced with the increasing of ozone dosage and the decreasing of nano-TiO₂ dosage, Br^? concentrations and the pH value. Possible BrO₃^? minimization mechanism was that nano-TiO₂ accelerated the decomposition of the dissolved O₃ into OH radicals, which rapidly generated H₂O₂, and reduced HOBr/OBr^? to Br^?.     

Large-Scale Experimental Validation of a Model for the Kinetics of Ozone and Hydroxyl Radicals with Natural Organic Matter

A unified model for the kinetics of O₃ and ^?OH with NOM was proposed, calibrated and validated based on large experimental data sets. Single-phase batch experiments were done on 11 water samples from seven resources. Seasonal variations were studied on three resources. Effects of reaction time with ozone, ozone dose, pH, temperature, radical scavenger adding, and NOM dilution were studied. The experiments represented more than 1200 and 900 concentration measurements, respectively, for ozone and pCBA (^?OH tracer). Mechanistic models were used for ozone self-decomposition and carbonate species kinetics. Results showed that the proposed model is robust and can handle different water characteristics and different experimental conditions: 75% of the experiments were modeled satisfactorily (for ozone and pCBA). Next, the domain of validity was determined: 6 ≤ pH ≤ 8; 1 meq.L^?1 ≤ alkalinity ≤ 6 meq.L^?1; 0–0.5 mgC.L^?1 ≤ TOC ≤ 3.1 mgC.L^?1. Only water samples with high organic (TOC > 2.4 mg.L^?1) and low inorganic contents (alkalinity < 0.3 meq.L^?1) could not be modeled adequately. Seasonal comparisons showed that the quality of the predictions decreases only for pCBA when having calibrated the model at another season. The model gave good results when using only 6 single batch experiments for calibration.     

Survey of Seawater Intrusion in the Pearl River Basin and Modeling Bromate Formation during Ozonation of the Raw Water

Bromate formation has been identified as a significant barrier in the application of ozone during water treatment the downstream region of the Pearl River Basin that contains high levels of bromide. Seawater intrusion will increase bromide concentration in the inshore surface water. In this study, seawater intrusion in the Pearl River Basin was surveyed and modeling bromate formation during ozonation of the raw water affected by seawater intrusion was studied. Bromate formation models were developed to simulate the effects of the characteristics of water quality and the operating parameters of treatment processes on bromate formation during preozonation process and postozonation process. The results show that the downstream of the Pearl River Basin is affected seriously by seawater intrusion and the bromide mainly comes from seawater. Some empirical models were developed to estimate the concentration of bromate in ozonated surface raw water affected by seawater intrusion during the treatment process.     

Destruction of Volatile Organic Contaminants in Drinking Water by Ozone Treatment

Controlled, pilot-plant ozone treatment tests were conducted on twenty-nine volatile organic contaminants in distilled water and groundwater. Results show that aromatic compounds and alkenes are well removed by ozone treatment, but that alkanes are poorly removed. Also, efficiency of destruction improved for the alkenes and aromatic compounds with increasing applied ozone dosage and, for some alkanes, with increasing pH. For most compounds, the efficacy of ozone was not severely affected by the background water matrix. Generally, information gathered from the literature regarding rate constants for the ozone treatment of compounds in the gaseous phase or in organic solution predicted, to a useful degree, the effectiveness of ozone in treating aqueous solutions in the present study.

Several of the test conditions selected for this preliminary study may be similar to those found in drinking water treatment plants. Consequently the findings of this research may help guide utilities in their choice of alternative treatments to meet Maximum Contaminant Levels for volatile organic contaminants such as trichloroethylene and benzene.     

Decomposition of Ozone in Highly Concentrated Aqueous Solutions Under semi-Commercial Conditions

The use of ozone in the treatment of drinking water in the form of a highly concentrated aqueous solution yields technological advantages compared with the traditional use of ozone in its gaseous state. However, for a comparative calculation of profitability, it is essential to know the ozone decomposition rate in the water solution in question. The present paper reports for the first time investigations with respect to this question under semi-commercial conditions and compares the results with laboratory tests made at another place.     

Formation of Bromate Ion Through a Radical Pathway in a Continuous Flow Reactor

The contribution of ozone and hydroxyl radical to the formation of bromate ion was investigated in a continuous flow reactor. Experiments were conducted under a wide range of ozone dose (0.7 ～ 3.8 mgL), pH (6.5 ～ 8.5), and t-butanol concentration (0 ～ 0.5 mM). The formation of bromate ion was found to depend on radical reaction pathway, because the amount of bromate ion formed increased with pH and decreased with t-butanol, a radical scavenger, even when dissolved ozone concentrations were almost the same. In fact, the amount of bromate ion formed was reduced by 90% in the presence of t-butanol. Furthermore, the formation of bromate ion occurred even when dissolved ozone was not significantly detected in the presence of organic matter (TOC of 1 mgCL). The second-order reaction rate constant of hydroxyl radical with bromide ion, k _HO,Br^? of 1.7 × 10⁹ (M^?1s^?1), was obtained on the assumption that the reactions of bromide ion and t-butanol with hydroxyl radical were competitive with each other in the presence of t-butanol and that the formation of bromate ion depended on the reaction of bromide ion with hydroxyl radical. Therefore, it is concluded that the reaction of bromide ion with hydroxyl radical dominated in the overall reaction from bromide ion to bromate ion in the continuous flow reactor.