Empirical modeling of bromate formation during ozonation of bromide-containing waters

Empirical bromate formation models were developed from observed batch ozonation data to simulate the effects of important water quality characteristics and treatment processes on bromate formation. Data generated from true batch ozonation studies with an orthogonal matrix design, served as the base for development of empirical models for bromate formation. The variables examined include pH, initial bromide concentration, alkalinity, ozone dose, ammonia and dissolved organic carbon level. This array of variables was selected to evaluate the effects of important water quality characteristics and treatment processes on the formation of bromate ion during water ozonation. Limited temperature variation data were also generated. Isolation and fractionation of natural organic matter (NOM) by ultrafiltration and reverse osmosis membrane techniques allowed assessment of source water variations and the role of molecular size on bromate formation. Multiple linear regression of logarithmic transformations was used to generate the models. Results obtained from the empirical models indicate that bromate formation is favored at high pH, initial bromide concentration, alkalinity and high ozone dose. On the other hand, increasing DOC and ammonia concentration decreased bromate formation. The models also indicated that NOM isolated from different water sources have a strong influence on bromate formation upon ozonation of model solutions composed of different membrane isolates. Both internal and external validation of the models demonstrated that the bromate models predicted bromate formation well. Finally, the models indicated that acid addition (pH depression) strategies can be used to control bromate formation.     

Impact of a magnetic ion exchange resin on ozone demand and bromate formation during drinking water treatment

The objective of this research was to examine the impact of a magnetic ion exchange resin (MIEX) on ozone demand and bromate formation in two different ozonated waters at bench scale. The first raw water had a high bromide ion concentration, a high ozone demand, and was highly colored. Based on experimental findings from the first water, the second water was selected as a model water in which more controlled experiments were performed. The waters were treated with the MIEX resin using jar test procedures to find the optimal MIEX dosage based upon the removal of ultraviolet (UV)-absorbing substances, dissolved organic carbon (DOC), and bromide. The optimal resin dosage was chosen for bulk MIEX treatment and subsequent ozonation in a semi-batch reactor. The ozone demand and formation of bromate were analyzed as a function of ozone dosage and dissolved ozone concentration for the MIEX pre-treated water, and compared to the results obtained by ozonating the water without MIEX pre-treatment. The results indicate that pre-treatment of the water with the MIEX resin significantly reduces total organic carbon, DOC, UV absorbance, color, and to some extent, bromide. MIEX pre-treatment of the water prior to ozonation substantially lowered the ozone demand and formation of bromate during subsequent ozonation.     

Disinfectant decay and disinfection by-products formation model development: chlorination and ozonation by-products

Comprehensive disinfectant decay and disinfection by-product formation (D/DBP) models in chlorination and ozonation were developed to apply to various types of raw and treated waters. Comparison of several types of models, such as empirical power function models and empirical kinetic models, was provided in order to choose more robust and accurate models for the D/DBP simulations. An empirical power function model based on dissolved organic carbon and other parameters (Empirically based models for predicting chlorination and ozonation by-products: haloacetic acids, chloral hydrate, and bromate, EPA Report CX 819579, 1998) showed a strong correlation between measured and predicted trihalomethane (THM) and haloacetic acid (HAA) formation for raw waters. Internal evaluation of kinetic-based models showed good predictions for chlorine decay and THM/HAA formation, but no significant improvements were observed compared to the empirical power function model simulations. In addition, several empirical models for predicting ozone decay and bromate (ozonation disinfection by-product) formation were also evaluated and/or developed. Several attempts to develop kinetic-based and alternative models were made: (i) a two-stage model (two separate decay models) was adapted to ozone decay and (ii) an ozone demand model was developed for bromate formation. Generally, internal evaluation of kinetic-based models for ozone decay showed significant improvements, but no significant improvements for the simulation of bromate formation were observed compared to the empirical power function model simulations. Additional efforts were performed to reduce the gaps between specific models and their actual application. For instance, temperature effects and configuration of ozone contactors were considered in actual application.     

Ozonation of drinking water: part II. Disinfection and by-product formation in presence of bromide,iodide or chlorine

Ozone is an excellent disinfectant and can even be used to inactivate microorganisms such as protozoa which are very resistant to conventional disinfectants. Proper rate constants for the inactivation of microorganisms are only available for six species (E. coli, Bacillus subtilis spores, Rotavirus, Giardia lamblia cysts, Giardia muris cysts, Cryptosporidium parvum oocysts). The apparent activation energy for the inactivation of bacteria is in the same order as most chemical reactions (35-50 kJ mol(-1)), whereas it is much higher for the inactivation of protozoa (80 kJ mol(-1)). This requires significantly higher ozone exposures at low temperatures to get a similar inactivation for protozoa. Even for the inactivation of resistant microorganisms, OH radicals only play a minor role. Numerous organic and inorganic ozonation disinfection/oxidation by-products have been identified. The by-product of main concern is bromate, which is formed in bromide-containing waters. A low drinking water standard of 10 microg l(-1) has been set for bromate. Therefore, disinfection and oxidation processes have to be evaluated to fulfil these criteria. In certain cases, when bromide concentrations are above about 50 microg l(-1), it may be necessary to use control measures to lower bromate formation (lowering of pH, ammonia addition). Iodate is the main by-product formed during ozonation of iodide-containing waters. The reactions involved are direct ozone oxidations. Iodate is considered non-problematic because it is transformed back to iodide endogenically. Chloride cannot be oxidized during ozonation processes under drinking water conditions. Chlorate is only formed if a preoxidation by chlorine and/or chlorine dioxide has occurred.     

Water quality factors affecting bromate reduction in biologically active carbon filters

Biological removal of the ozonation by-product, bromate, was demonstrated in biologically active carbon (BAC) filters. For example, with a 20-min EBCT, pH 7.5, and influent dissolved oxygen (DO) and nitrate concentrations 2.1 and 5.1 mg/l, respectively, 40% bromate removal was obtained with a 20 microg/l influent bromate concentration. In this study, DO, nitrate and sulfate concentrations, pH, and type of source water were evaluated for their effect on bromate removal in a BAC filter. Bromate removal decreased as the influent concentrations of DO and nitrate increased, but bromate removal was observed in the presence of measurable effluent concentrations of DO and nitrate. In contrast, bromate removal was not sensitive to the influent sulfate concentration, with only a slight reduction in bromate removal as the influent sulfate concentration was increased from 11.1 to 102.7 mg/l. Bromate reduction was better at lower pH values (6.8 and 7.2) than at higher pH values (7.5 and 8.2), suggesting that it may be possible to reduce bromate formation during ozonation and increase biological bromate reduction through pH control. Biological bromate removal in Lake Michigan water was very poor as compared to that in tapwater from a groundwater source. Bromate removal improved when sufficient organic electron donor was added to remove the nitrate and DO present in the Lake Michigan water, indicating that the poor biodegradability of the natural organic matter may have been limiting bromate removal in that water. Biological bromate removal was demonstrated to be a sustainable process under a variety of water quality conditions, and bromate removal can be improved by controlling key water quality parameters.     

基于BP人工神经元网络的臭氧生物活性炭系统建模研究

针对臭氧生物活性炭系统的特点和研究中的难点，创新地引入人工神经元网络的理论和思想，提出该过程的人工神经网络的分析方法。通过建立基于ＢＰ人工神经元网络的臭氧生物活性炭系统模型，考察该网络对水处理系统建模的适应性，探讨了臭氧生物活性炭系统中影响因素之间的关系，为提高臭氧生物活性炭系统的应用水平和实现水处理系统的在线控制 一条可行途径。     

臭氧消毒中溴酸盐的形成、检测与控制

用臭氧对含溴化物的饮用水进行消毒时会生成溴酸盐副产物，溴酸盐被国际癌症研究机构定为2B级（具有较高的致癌可能性）潜在致癌物。臭氧氧化溴化物生成溴酸盐要经过多步反应，控制溴酸盐生成的方法有加氨、降低pH值、投加活性炭、投加高锰酸盐和增加臭氧投加点的数量等。用臭氧消毒的最终目的是杀灭致病菌，因此如何找到臭氧、致病菌、溴酸盐消毒副产物之间的最佳平衡点还有待进一步研究。     

Modeling Cryptosporidium parvum oocyst inactivation and bromate in a flow-through ozone contactor treating natural water

A reactive transport model was developed to simultaneously predict Cryptosporidium parvum oocyst inactivation and bromate formation during ozonation of natural water. A mechanistic model previously established to predict bromate formation in organic-free synthetic waters was coupled with an empirical ozone decay model and a one-dimensional axial dispersion reactor (ADR) model to represent the performance of a lab-scale flow-through ozone bubble-diffuser contactor. Dissolved ozone concentration, bromate concentration (in flow-through experiments only), hydroxyl radical exposure and C. parvum oocyst survival were measured in batch and flow-through experiments performed with filtered Ohio River water. The model successfully represented ozone concentration and C. parvum oocyst survival ratio in the flow-through reactor using parameters independently determined from batch and semi-batch experiments. Discrepancies between model prediction and experimental data for hydroxyl radical concentration and bromate formation were attributed to unaccounted for reactions, particularly those involving natural organic matter, hydrogen peroxide and carbonate radicals. Model simulations including some of these reactions resulted in closer agreement between predictions and experimental observations for bromate formation.     

Residual oxidant decay and bromate formation in chlorinated and ozonated sea-water

Oxidant decay and bromate formation were studied under light and dark conditions in 5.15 and 30‰ artificial sea-water and 5‰ natural estuarine water following ozonation or chlorination. For both oxidants, light exposure accelerated the residual oxidant decay rates which were inversely related to sample salinities in artificial sea-water. Significant quantities of bromate were produced in light-exposed, chlorinated samples with an initial residual oxidant concentration of 70 μM (5mg l⁻¹ as total residual chlorine) but not at lower residual oxidant concentrations or in non-photolyzed samples. No bromate was formed in any of the chlorinated natural estuarine water samples. Bromate production was much greater in ozonated samples than in chlorinated ones and was formed in two distinct stages. Photolytic bromate formation decreased with increasing bromide concentration in both chlorinated and ozonated artificial sea-water. Bromate formation was completely inhibited in the presence of NH₃-N and estuarine sediment. The same free radical mechanism is proposed for both ozone-induced and photolytic-induced bromate formation in artificial sea-water.     

Inactivation of Bacillus subtilis spores and formation of bromate during ozonation

Inactivation of B. subtilis spores with ozone was investigated to assess the effect of pH and temperature, to compare the kinetics to those for the inactivation of C. parvum oocysts, to investigate bromate formation under 2-log inactivation conditions, and to assess the need for bromate control strategies. The rate of B. subtilis inactivation with ozone was independent of pH, decreased with temperature (activation energy of 42,100 Jmol(-1)), and was consistent with the CT concept. B. subtilis was found to be a good indicator for C. parvum at 20-30 degrees C, but at lower temperatures B. subtilis was inactivated more readily than C. parvum. Bromate formation increased as both pH and temperature increased. For water with an initial bromide concentration of 33 microgl(-1), achieving 2-logs of inactivation, without exceeding the 100 microg l(-1) bromate standard, was most difficult at 30 degrees C for B. subtilis and at midrange temperatures (10-20 degrees C) for C. partum. pH depression and ammonia addition were found to reduce bromate formation without affecting B. subtilis inactivation, and may be necessary for waters containing more than 50 microgl(-1) bromide.     

ZSM-5沸石削减臭氧氧化过程中的溴酸根生成量

分别采用超纯水、硼酸盐缓冲溶液和自来水配制含溴离子水,考察投加不同硅铝比的ZSM-5沸石对臭氧氧化过程中溴酸根生成量的削减效果及机理.结果表明,在三种不同介质中,ZSM-5沸石对溴酸根生成量的削减效果依次为:超纯水>硼酸盐缓冲溶液>自来水;硅铝比为300的ZSM-5沸石的削减效果最好,在硼酸盐缓冲溶液体系中,反应30min后可使溴酸根的生成量减少66%.硅铝比为300的ZSM-5沸石对溴离子和溴酸根均无明显的吸附作用,但可显著减少臭氧分解过程中的H_2O_2产量,这是其削减溴酸根生成量的主要原因.     

The removal of estrogenic activity and control of brominated by-products during ozonation of secondary effluents

The purposes of this study were to investigate the behavior of brominated by-products, such as bromate ion and total organic bromide, formed during ozonation for the removal of estrogenic activity in sewage effluents and to propose operation parameters for the ozonation process. It is necessary to reduce the E(2) equivalent concentration of estrogenic activity in secondary effluent treated by 90% of the initial one. To do so, ozonation until dissolved ozone concentration increased to 0.1mg/L (which corresponds to approximately 1mg O(3)/mg DOC(0) [consumed ozone per initial DOC] of consumed ozone for the effluent in this study) is proposed as an operation parameter for ozonation without the formation of brominated by-products.     

Ozone and the Formation of Bromate in Water Treatment

The ozonation of water is widely used within the drinking-water industry. The improvement of the performance of the Barcombe water-treatment works is envisaged. An ozonation stage and granular activated carbon filtration are being considered as an addition to the existing plant. As part of the investigation work, the influence of ozone on bromate formation was studied using a 3 m³/h pilot plant. The bromate production was found to depend upon (a) the applied ozone dose, (b) the contact period, and (c) the pH.
Using ozone in an appropriate way will be of benefit to the treatment process as well as meeting the new World Health Organization health guidelines for drinking water.     

Chlorination of bromide-containing waters: Enhanced bromate formation in the presence of synthetic metal oxides and deposits formed in drinking water distribution systems

Bromate formation from the reaction between chlorine and bromide in homogeneous solution is a slow process. The present study investigated metal oxides enhanced bromate formation during chlorination of bromide-containing waters. Selected metal oxides enhanced the decay of hypobromous acid (HOBr), a requisite intermediate during the oxidation of bromide to bromate, via (i) disproportionation to bromate in the presence of nickel oxide (NiO) and cupric oxide (CuO), (ii) oxidation of a metal to a higher valence state in the presence of cuprous oxide (Cu₂O) and (iii) oxygen formation by NiO and CuO. Goethite (α-FeOOH) did not enhance either of these pathways. Non-charged species of metal oxides seem to be responsible for the catalytic disproportionation which shows its highest rate in the pH range near the pK_a of HOBr. Due to the ability to catalyze HOBr disproportionation, bromate was formed during chlorination of bromide-containing waters in the presence of CuO and NiO, whereas no bromate was detected in the presence of Cu₂O and α-FeOOH for analogous conditions. The inhibition ability of coexisting anions on bromate formation at pH 8.6 follows the sequence of phosphate >> sulfate > bicarbonate/carbonate. A black deposit in a water pipe harvested from a drinking water distribution system exerted significant residual oxidant decay and bromate formation during chlorination of bromide-containing waters. Energy dispersive spectroscopy (EDS) analyses showed that the black deposit contained copper (14%, atomic percentage) and nickel (1.8%, atomic percentage). Cupric oxide was further confirmed by X-ray diffraction (XRD). These results indicate that bromate formation may be of concern during chlorination of bromide-containing waters in distribution systems containing CuO and/or NiO.     

Ozone decomposition of 2-methylisoborneol (MIB) in adsorption phase on high silica zeolites with preventing bromate formation

This work elucidates the applicability of our newly developed adsorptive ozonation process for the decomposition of 2-methylisoborneol (MIB), a typical taste and odor chemical, without the formation of possibly carcinogenic bromate ions. First, zeolite adsorbents were screened for their ability to adsorb MIB with a batch-type adsorption experimental apparatus and a flow-type decomposition experimental apparatus included an adsorbent-packed column. The USY zeolite with the highest silica to alumina ratio (SiO(2)/Al(2)O(3) molar ratio=70) showed the best performance as an adsorbent. Using this adsorbent, an ozonation experiment on an MIB solution including bromide ions was performed under various retention times using the flow-type apparatus. As a result, sufficient decomposition of MIB was achieved with preventing bromate formation.     

Formation of aldehydes upon ClO2 disinfection

Carbonyl compounds are considered to be the most common ozonation by-products. Apart from well-known chlorites and chlorates, chlorine dioxide (ClO(2)) also generates organic by-products. The goal of this paper is an investigation into the influence of disinfection with ClO(2) on the aldehydes formation. Three types of waters were disinfected with different doses of ClO(2) at the various pH values. The results of size exclusion chromatography show that the reaction of ClO(2) with humic fraction of natural organic matter proceeds mainly on an aromatic part of the molecules. The results obtained indicate that the level of carbonyls concentration can significantly increase with the time of ClO(2) reaction with carbonyl precursors in treated water. There is no noticeable correlation between quantity of aldehydes and pH value of disinfected water. The range of "productivity" of aldehydes in water treated with chlorine dioxide is similar to the range estimated for the carbonyls formed upon ozonation.     

N-nitrosodimethylamine (NDMA) formation during ozonation of dimethylamine-containing waters

Ozonation of aqueous solutions of dimethylamine (DMA) leads to the formation of nitrosodimethylamine (NDMA). The yield of reaction is low (below 0.4% in relation to DMA) and increases with increasing pH. Contact time, ozone/DMA ratio and radical scavengers are other variables controlling the yield of reaction. Data from the literature and observed ozonation by-products suggest that nitrosation of DMA might be responsible for nitrosamine generation. NDMA can be recognized as a by-product of ozonation of DMA in water, which is formed in a specific, but reasonable, range of ozone/DMA ratios. The reaction may have potential importance for water treatment technology assuming reasonable micrograms per liter of DMA concentrations in raw waters.     

Effects of temperature and chemical addition on the formation of bromoorganic DBPs during ozonation

The effects of temperature and addition of OH radical scavengers/enhancers or HOBr scavenger on the formation of bromoorganic disinfection byproducts (DBPs) from ozonation of six raw waters were studied in true batch reactors. The formation of bromoorganic DBPs during ozonation generally increased with the increase of temperature, but might also decrease for the waters with somewhat higher values of specific UV absorbance (SUVA). The addition of hydrogen peroxide, ethanol, or ammonium dramatically decreased the formation of bromoorganic DBPs; t-butanol addition significantly increased the formation of bromoorganic DBPs; bicarbonate addition might increase or decrease bromoorganic DBP formation depending on the water source. For all the waters treated with the chemical addition, the level of total organic bromine (TOBr) varied with the same pace as that of ozone exposure (CT), which suggests that TOBr formed during ozonation may be used to estimate the CT, a measure for the achieved degree of disinfection. The results demonstrate that for each water, the correlation between TOBr and CT was less affected by the change of chemical composition of the water than that between BrO(3)(-) and CT; for a given chemical composition and temperature of a water, there generally were well-defined relationships between TOBr and CT, and bromoform and CT just as that between BrO(3)(-) and CT. The possible mechanisms behind the linear functions of TOBr or BrO(3)(-) versus CT were given. Further study is needed to examine whether the trends found in this research can be applicable for the high SUVA waters.     

The use of artificial neural networks in adiabatic curves modeling

Adiabatic hydration curves are the most suitable data for temperature calculations in concrete hardening structures. However, it is very difficult to predict the adiabatic hydration curve of an arbitrary concrete mixture. The idea of modeling adiabatic temperature rise during concrete hydration with the use of artificial neural networks was introduced in order to describe the adiabatic hydration of an arbitrary concrete mixture, depending on factors which influence the hydration process of cement in concrete. The influence of these factors was determined by our own experiments. A comparison between experimentally determined adiabatic curves and adiabatic curves, evaluated by proposed numerical model shows that artificial neural networks can be used to predict adiabatic hydration curves effectively. This model can be easily incorporated in the computer programs for prediction of the thermal fields in young concrete structures, implemented in the finite element or finite difference codes. New adiabatic hydration curves with some other initial parameters of the concrete mixture can be easily included in this model in order to expand the range of suitability of artificial neural networks to predict the adiabatic hydration curves.     

Biofiltration for removal of BOM and residual ammonia following control of bromate formation

Nitrification was developed within a biological filter to simultaneously remove biodegradable organic matter (BOM) and residual ammonia added to control bromate formation during the ozonation of drinking water. Testing was performed at pilot-scale using three filters containing sand and anthracite filter media. BOM formed during ozonation (e.g., assimilable organic carbon (396-572 microg/L), formaldehyde (11-20 microg/L), and oxalate (83-145 microg/L)) was up to 70% removed through biofiltration. Dechlorinated backwash water was required to develop the nitrifying bacteria needed to convert the residual ammonia (0.1-0.5 mg/L NH(3)-N) to nitrite and then to nitrate. Chlorinated backwash water resulted in biofiltration without nitrification. Deep-bed filtration (empty-bed contact time (EBCT) = 8.3 min) did not enhance the development of nitrification when compared with shallow-bed filtration (EBCT = 3.2 min). Variable filtration rates between 4.8 and 14.6 m/h (2 and 6 gpm/sf) had minimal impact on BOM removal. However, conversion of ammonia to nitrite was reduced by 60% when increasing the filtration rate from 4.8 to 14.6 m/h. The results provide drinking water utilities practicing ozonation with a cost-effective alternative to remove the residual ammonia added for bromate control.