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.     

溴酸钾作为面包添加剂的使用及安全回顾

在过去的几年中,人们给予溴酸钾以极大关注,对其在面团及面包中作为氧化剂使用的安全问题提出质疑。本就溴酸钾自1914年初次在美国使用以来的情况,以及20年以来对于溴酸钾安全问题的研究进行了回顾。结论是溴酸钾是一种毒害基因的致癌物并因而被世界卫生组织禁用。世界上的许多国家都已经禁止了溴酸钾的作用,但是在中国溴酸钾仍被列为面粉处理剂,允许以0．03g/kg的用量于小麦面粉中使用。许多禁用溴酸钾的国家经实践证明,用抗坏血酸、酶制剂及乳化剂的混合物可以替代溴酸钾,但价格更贵。当食品安全及消费的健康岌岌可危时,人们应当提高警惕了。     

Minimizing Bromate Concentration by Controlling the Ozone Reaction Time in a Full-Scale Plant

The latest European Directive 98/83/CE (5 December 1998), concerning the quality of water intended for human consumption, has set a two-stage parametric value for bromate. Bromate concentration will comply with 25 μg/L after December 25, 2003, and with 10 μg/L after December 25, 2008. Bromate formation in water is generally due to bromide oxidation during the ozonation stage. Due to higher temperatures, this latter parametric value is often exceeded in summer. Minimizing bromate levels is thus a crucial problem for drinking water producers. A bromate-minimizing strategy consists of shortening the reaction time between ozone and water. This can be done by neutralizing dissolved ozone residual with bisulfite at the exit of the ozone reactor chamber and/or by managing the introduction of ozone in different chambers depending on the water flow rate. This is only possible if, in our case, the disinfection goal for ozone is respected toward bacteria and viruses. The CT value must comply with 1.6 mg/min/L. In our plants, this value could be very large due to high contact time in and after leaving the ozone reactors.     

Ozonation Of Seawater - Applicability Of Ozone For Recycled Hatchery Cultivation

It is known that oxidants remaining in ozonated seawater give harmful effects to fishes. This is one of the reasons restricting applications of ozone for disinfection and quality improvements of seawater used in hatcheries. In this study, fatal doses of the oxidants to larvae, reduction of the residual oxidants by activated carbon unit, and the possibility of recycled seawater in a hatchery using ozone and activated carbon were preliminarily investigated.

The residual oxidants were very harmful to larvae, and their reduction was indispensable to the cultivations. The oxidants were found to be easily removed by contacting with activated carbon. Ozonation in cooperation with sand and activated carbon filtrations was suggested to be effective for improving the rate of survival and water quality. It was also suggested that the oxidants were alternative to predicted the BrO or BrO₃ ions.     

Degradation of Pesticides by Ozonation and Advanced Oxidation

In the Netherlands many water supply companies are upgrading their surface water treatment plants in order to guarantee the water supply and water quality in the coming years. The Water Supply Company North West Brabant (WNWB) has plans to upgrade their treatment plant at Zevenbergen. In the retrofit plant chlorination will be abandoned and probably ozonation will be the major barrier against microorganisms. Pesticide concentrations will be decreased by three barriers: storage, ozonation and activated carbon filtration.

If the ozone dosage is restricted just to reach the required disinfection level at pH 7.2, ozonation is a poor barrier against pesticides. Out of 23 selected pesticides, only 6 were effectively degraded: dimethoate, chlortoluron, diuron, isoproturon, metoxuron and vinclozolin (O₃/DOC = 0.55 g/g). Application of an (O₃/DOC ratio of 1.0 g/g results in an effective barrier for roughly 50% of the tested pesticides (also for diazinon, parathion-methyl, linuron, methabenzthiazuron, metobromuron, MCPA and MCPP). Pesticides were degraded more effectively at high pH and high temperature.

For additional degradation of high concentrations of persistent pesticides, advanced oxidation may be applied. Atrazine, propazine, simazine, chlor-fenvinphos, tetrachlorvinphos, 2,4-D, 2,4-DP and 2,4,5-T were degraded by O₃/DOC = 1.4 g/g and H₂O₂/O₃ = 0.5 g/g. Dicamba and dikegulac were most persistent. pH has a minor effect on the degradation of pesticides by advanced oxidation. Higher hydrogen peroxide dosages showed no improvement in degradation. After ozonation and advanced oxidation, about 50% of totally reacted atrazine and propazine was converted into desethylatrazine. No desisopropylatrazine formation was observed.     

Practical Studies of the Electrolysis and Volatilization of the Bromide from Drinking Water to Minimize Bromate Production by Ozonation

In four recently published articles, a process for the oxidation of bromide to bromine and the volatilization of bromine from drinking water sources was presented. This process was shown to be able to remove up to 35% percent of the bromide found naturally in the California State Water Project. Although bromide itself is quite harmless, it has been shown to react with commonly used disinfectants to produce compounds or disinfection by-products (DBPs) of suspected carcinogens. Bromide reacts with ozone to form bromate. This article presents two studies of pilot scale, flow-through electrolytic reactors that oxidize bromide to bromine and volatilize bromine at <pH 3.5, which occurs at the anode as a result of the oxidation of water. One reactor had 14 anodes that were 91 cm deep and the other had 13 anodes 1.2 cm deep. The bromide removal rates were studied at several different water flows and power settings for different bromide concentrations for both reactors. The results show removal of bromide is impacted by water flows and power settings for different bromide concentrations. Effluent from the deep reactor did show some reduction in bromate concentration as compared to control samples but the results were inconsistent. This appeared to be caused by significant differences in the ozone demand produced by different experimental conditions, difficulty determining the concentration of chlorine, and the use of hydrogen peroxide as a dechlorinating agent. Using the shallow reactor, these difficulties were overcome by developing a more consistent determining chlorine concentration, using much larger ozone doses to overwhelm the ozone demand, and by using ascorbic acid instead of hydrogen peroxide. With these changes, it could be shown that the electrolytic reactor not only lowered the concentration of bromide in the water but when ozonated, the amount of bromate formed was reduced in direct proportion to the amount of bromide removed for an equal dose of ozone.     

Modeling of bromate formation by ozonation of surface waters in drinking water treatment

The main objective of this paper is to try to develop statistically and chemically rational models for bromate formation by ozonation of clarified surface waters. The results presented here show that bromate formation by ozonation of natural waters in drinking water treatment is directly proportional to the "Ct" value ("Ctau" in this study). Moreover, this proportionality strongly depends on many parameters: increasing of pH, temperature and bromide level leading to an increase of bromate formation; ammonia and dissolved organic carbon concentrations causing a reverse effect. Taking into account limitation of theoretical modeling, we proposed to predict bromate formation by stochastic simulations (multi-linear regression and artificial neural networks methods) from 40 experiments (BrO(3)(-) vs. "Ctau") carried out with three sand filtered waters sampled on three different waterworks. With seven selected variables we used a simple architecture of neural networks, optimized by "neural connection" of SPSS Inc./Recognition Inc. The bromate modeling by artificial neural networks gives better result than multi-linear regression. The artificial neural networks model allowed us classifying variables by decreasing order of influence (for the studied cases in our variables scale): "Ctau", [N-NH(4)(+)], [Br(-)], pH, temperature, DOC, alkalinity.     

The Reactions of Bromide with Ozone Towards Bromate and the Hypobromite Puzzle: A Density Functional Theory Study

Taking the solvent water into account, the energetics of the reactions of O₃ with Br^? leading to BrO₃ ^? have been calculated by Density Functional Theory at the B3LYP/6–311+G(d)/SCRF =COSMO level. Br^? reversibly forms an adduct, BrOOO^?, (ΔG?=?+6 kJ mol^?1) that decays spin allowed into BrO^? and O₂(¹Δ_g) (ΔG?=?+13 kJ mol^?1). BrO^? undergoes an oxidation to BrO₂ ^? and a reduction to Br^?. This may be accounted for if two different adducts, OBrOOO^? and BrOOOO^?, decay into BrO^? plus O₂ and Br^? plus 2 O₂. After cyclization, OBrOOO^? may also lead to Br^? plus 2 O₂.     

Adsorptive ozonation of 2-methylisoborneol in natural water with preventing bromate formation

This paper presents an application of our newly developed adsorptive ozonation process using a high silica zeolite adsorbent (USY) for drinking water treatment. First, the adsorption of 2-methylisoborneol (2-MIB) on USY in a river water/pure water mixture was clarified by a batch-type adsorption experiment. The results showed that 2-MIB was adsorbed on USY; however, almost all of the adsorbed 2-MIB was desorbed over time. The desorption rate was increased with the ratio of river water to pure water, indicating that compounds dissolved in the river water, such as natural organic matter (NOM), prevent the adsorption of 2-MIB on USY. Second, the ability of the river water to consume ozone was confirmed in an experiment using a USY-packed column reactor. The ozone consumption was obviously increased by the presence of USY, indicating that USY-adsorbing compounds dissolved in the river water (probably small size NOM) consumed the ozone. However, the rapid ozone consumption was occurred by 6-8 s in the retention times when 3.14-4.38 mgL(-1) of water dissolved ozone was fed, this rapid ozone consumption lasted no more than these times. This result revealed that the rapid consumption of ozone by the adsorptive compounds in our process could be avoided within a certain retention time (6-8 s; especially for the river water used in this study) when enough concentration of ozone (3.14 mgL(-1) or more; same above) was supplied. We therefore performed a trial in which 2-MIB dissolved in river water was continuously decomposed using a USY-packed column with various ozone concentrations. In the process, the adsorptive compound dissolved in the river water adsorbed and reacted with ozone in the parts of the apparatus upstream of the column, while the adsorption and decomposition of 2-MIB took place in the parts of the apparatus downstream of the column. This resulted in a sufficient 2-MIB decomposition with minimizing bromate ion formation.     

溴酸钾的安全问题及其替代途径

在全球范围内,广大消费者和大多数政府对食品质量和安全问题的认识在不断提高,对于食品的标准、质量、卫生以及对食品添加剂、农药残留和污染物等的安全性评价越来越重视。随着安全性评价的不断深入,检测技术的不断进步,某些食品添加剂对人体健康的潜在危害性得以揭示,从而迫使人们对其安全性进行重新认识。作为面粉调节剂主要用于面包生产的溴酸钾,就是这样一个从曾经广泛使用到严格限制,直至被逐浙禁止使用的例子。