Formaldehyde Formation During Ozonation Of Drinking Water

Partial oxidation of natural organic material during ozonation produces oxygenated by-products of low molecular weight. Formaldehyde, being the most common oxygenated by-product of ozone, is considered to be a problematic compound by the water industry due to its potential adverse health effects. This research attempts to provide specific information on the effects of water quality parameters, specifically, pH and alkalinity, the structure of humic material, and the operational parameters, e.g., ozone dosage and contact time, on generation of formaldehyde. The results showed that ozonation caused almost an immediate formation of formaldehyde, which reached a peak value, and then started to decrease with continued ozonation. Ozonation of aqueous fulvic acid produced higher concentrations of formaldehyde compared to other types of humic material. Formaldehyde formation was suppressed by high bicarbonate levels, and enhanced at higher pH. Formaldehyde accumulation was more dramatic at low ozone dosages.     

Effect of Ozone and GAC Process for the Treatment of Micropollutants and DBPs Control in Drinking Water: Pilot Scale Evaluation

To improve the quality of water supplied to the City of Seoul in Korea, a pilot-scale evaluation of how the conventional treatment process could be upgraded was conducted. Three candidate processes were evaluated and compared: a conventional process (consisting of coagulation, sedimentation, and rapid sand filtration) plus GAC (Train A); a conventional process plus ozone and GAC (Train B); and a process consisting of coagulation, sedimentation, intermediate ozone, sand filtration, and GAC (Train C). Treatment efficiency of the unit process and overall treatment trains were evaluated using several parameters such as turbidity, dissolved organic carbon (DOC), UV absorbance at 254 nm (UV₂₅₄), specific ultraviolet absorbance (SUVA), micropollutants (pesticides, benzenes, and phenols), disinfection by-products (trihalomethanes (THMs), haloacetic acids (HAAs) and aldehydes), and total organic halogen (TOX). Results showed that ozone and/or GAC was effective for removing micropollutants and controlling chlorinated by-products such as THMs and HAAs. However, any synergistic effect of ozonation (adsorption and biodegradation) on GAC was observed due to the low concentration of aldehydes in raw and process water.     

Changes in Ozone Demand of Water During the Treatment Process

The protocol for the measurement of ozone demand of water and the change in the dissolved ozone residual with time, using the Gas Ozone Test (GOT) was applied in monitoring water quality of two water treatment facilities. The change in the ozone concentration of water as a function of time was measured for each sample. The resulting half-time was correlated with the ozone dosage, although this parameter does not appear to be directly linked to the characteristics of the water samples studied. The change in the ozone concentration of water as a function of time and ozone dose, measured by the GOT, has direct applications in the sizing of ozonation reactors.     

Oxidation of Cyanuric Acid in Aqueous Solution by Catalytic Ozonation

The aim of this work was studying the activity of a Ru/CeO₂ powder catalyst in the ozonation of aqueous solution of cyanuric acid (CYA). Ozonation in the presence of the catalyst significantly enhances CYA degradation. Within this work, investigation of the influence of pH and initial concentration on the catalytic ozonation of CYA has been done in a semicontinuous reactor. The removing degree of CYA at pH 5.9 show better response in comparison to pH 2.5 and pH 8.2. The mineralization of CYA by catalytic ozonation formed nitrate ions (0.7 mol of NO₃^?/mol of CYA removed for 50% initial CYA abatement) and nitrite and ammonium ions in small amounts. Three transformation products formed during catalytic ozonation were identified from LC/MS and MS/MS analyses. The impact of oxidation on the toxicity was measured from the inhibition of Vibrio fisheri, which was found to increase continuously.     

Formation of Ketoacids in Ozonated Drinking Water

Three ketoacids; glyoxylic acid, pyruvic acid and ketomalonic acid, were identified in ozonated drinking waters and fulvic acid solutions using gas chromatography-mass spectrometry. It was found that the concentrations of ketoacids were much higher than those of aldehydes in ozonated waters. The significance of ketoacids in finished drinking waters is discussed.     

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.     

Worldwide Ozone Capacity for Treatment of Drinking Water and Wastewater: A Review

One question often raised when ozone professionals gather is “How much ozone capacity is installed?” Although the use of ozone for industrial purposes is growing, the largest use for ozone resides in the use of treatment of municipal drinking and wastewater. It is very difficult to summarize ozone capacity for industrial applications as much data are kept confidential. A number of reports have been published over the years on installed ozone capacity. Ozone capacity estimation is a moving target as plants are built and others removed from service for a number of reasons. This paper summarizes, using data available, ozone capacity for drinking water and wastewater. Focus is on the United States, Canada, Europe and Japan. IOA members and member companies are encouraged to submit additional data to enable this summary to be as accurate and relevant as possible.     

Conditions Affecting Bromate Formation During Ozonation of Bottled Water

Bromate concentration, ozone lifetime and ozone exposure (CT value) measured in bottled water in full-scale runs, were in good agreement to those measured in laboratory experiments. Ozone lifetime in bottled water was high enough to result in a CT value greater than 5 even for ozone dose as low as 0.1?mgO₃/L, at a water pH of 7.6. Bromate was gradually formed during the ozone lifetime. Bormate formation and ozone exposure were significantly influenced by pH. In full-scale runs, an ozone dose of 0.15?mgO₃/L at pH=7.6 resulted in a CT of 10.3 and a bromate concentration of 13.5?µg/L, while at pH=7.25 the values of CT and BrO₃ ^? were 12.6 and 9.6?µg/L, respectively. By decreasing further the pH to 6.8, an increase of CT value to 15.8 and a reduction of bromate to 5.5?µg BrO₃ ^?/L were observed. In addition, results in full-scale runs showed that ozone exposure and bromate concentrations were linearly related to ozone dose in the working range of 0.1 to 0.25?mgO₃/L.     

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.     

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.     

Ozonation of Drinking Water: A Design Methodology

The formation of potentially carcinogenic organic halides has been shown to result from drinking water disinfection with chlorine. xidative treatment of organic halide precursors with ozone prior to chlorination has surfaced as an attractive technique for reducing the formation of these compounds. In addition to reduction of precursor levels, preozonation has been reported to effect other beneficial results in water treatment. This paper presents design methodologies to optimize the implementation of the ozonation process for water treatment applications. Pre-design considerations common to all ozonation design processes are discussed. Subsequently, design procedures for the ozone generation and contacting systems are reviewed.     

Rationales for Multiple Stage Ozonation in Drinking Water Treatment Plants

Starting in the early 1970s, the application of ozone for drinking water treatment began to evolve from primarily single-purpose, single-stage use for disinfection, taste and odor control or iron and manganese oxidation, to multipurpose uses of ozone. As a result, most of the newer drinking water treatment plants have installed two- and even three-stages of ozonation. in order to maximize the technological benefits of ozone and to minimize the costs involved.     

Impact of Support Media on the Biological Treatment of Ozonated Drinking Water

An extensive review of the technical literature was conducted in order to determine the advantages and disadvantages of the various media used for biological filtration of ozonated drinking water. Granular activated carbon (GAC) filters were found to be significantly more efficient than conventional filters such as sand and anthracite coal. The type of activated carbon also impacted the performance of biofilters; due to their greater adsorption capacity, microporous GACs were found to be better suited than macroporus GACs.     

An Assessment of the Benefits Afforded by the Continuous Versus Intermittent Operation of Ozone for Drinking Water Treatment

Stricter regulation by OFWAT has encouraged water companies to optimize all stages of the water treatment process. This work reviews the ozonation process, in order to evaluate the benefits and disadvantages of continuous versus intermittent ozone operation. Two Advanced Water Treatment Works (AWTW) were surveyed, Farmoor AWTW, Which involves traditional (chemical) treatment processes, and Kempton Park AWTW, which incorporates slow sand filter sandwich? beds. Both reviews indicated that continuous ozone operation would result in an optimized solution based on dependability of ozone plant, reliability of water quality and cost efficiency.     

Changes in the Chemical Nature of a Biologically Treated Wastewater During Disinfection by Ozone

Pilot plant studies were carried out on the effect of ozone on the chemical content of a secondary domestic and industrial sewage. Results are expressed in terms of COD, BOD₅, nitrite ion concentrations, bacterial counts, XAD-4-extraetable compounds, and free amino acid concentrations. Ozone dosages of 6 to 12 mg/L were found to reduce levels of fecal bacteria, COD and nitrite ion concentrations significantly, to modify the nature and the concentration of XAD-4-extraetable compounds, and to increase the concentration of free amino acids.     

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.     

Pilot Study on Pre-Ozonation Enhanced Drinking Water Treatment Process

The enhancement of TOC, COD_Mn, and UV₂₅₄ reduction in the conventional drinking water treatment process by pre-ozonation was investigated in South China on treating dam source water with a pilot plant consisting of pre-ozonation, coagulation-sedimentation, and filtration units. Pre-ozonation enhanced the reduction of NOM in the conventional coagulation-sedimentation and filtration process, and the total removals of UV₂₅₄, COD_Mn and TOC were improved for 34.6%, 18.1% and 15.3%, respectively by the adoption of pre-ozonation under an ozone dose (in ozone consumption base) of 0.85 mg/L. The enhancement of UV₂₅₄ and COD_Mn removals was mainly achieved through direct ozonation on humic substances, and that for TOC removal was achieved through biodegradation in sand filtration. In comparison with the TOC removal of 38%, a removal of 49% was acquired for SDS-THM under a pre-ozonation dose of 0.80 mg/L, indicating the selective removal of THMFP. The reduction of SDS-THM paralleled the reduction of COD_Mn to a significant degree, suggesting that the COD_Mn might be an effective surrogate parameter for SDS-THM if the raw water does not contain the reductive inorganic matters. Although the source water contains 13.2–27.0μg/L bromide, the formation of bromate was negligible when the ozone dose was below 1.0 mg/L.     

Influence of Carbonate on the Ozone/Hydrogen Peroxide Based Advanced Oxidation Process for Drinking Water Treatment

The influence of carbonate on the ozone/hydrogen peroxide process has been investigated. Carbonate radicals, which are formed from the reaction of bicarbonate/carbonate with OH radicals, act as a chain carrier for ozone decomposition due to their reaction with hydrogen peroxide. The efficiency of bicarbonate/carbonate as a promoter for the radical-based chain reaction in presence of hydrogen peroxide has been calibrated and compared to a well-known chain promoter (methanol) and an inhibitor (tert-butanol). Relative to tert-butanol, the hydrogen peroxide induced ozone decomposition is accelerated by bicarbonate/carbonate. Relative to methanol, bicarbonate/carbonate in presence of hydrogen peroxide is less effective as a promoter under comparable experimental conditions.     

Effects Of Ozone On The Production Of Biodegradable Dissolved Organic Carbon (BDOC) During Water Treatment

This article deals with the oxidation effect of ozone on the increasing fraction of biodegradable organic matter with the “ozotest” method, a laboratory technique which simulates the effect of ozonation and allows a complete oxidation assessment. Ozone treatment was performed on river water samples and sand filter effluent samples. Ozone consumption, reduction of UV absorbance and BDOC formation were monitored with applied ozone doses from 0 to 10 mg/L and with contact times from 0 to 60 min. The BDOC formation was optimum at an applied ozone dose of 0.25-0.5 mg O₃ per mg DOC (contact time = 5 min) corresponding to apparition of traces of residual ozone and maximum UV reduction. Maximum ozone consumption, UV reduction and BDOC formation occurred simultaneously during the first two minutes of treatment. Concerning BDOC formation, applied ozone dose showed a greater effectiveness than contact time. For the same quantity of consumed ozone, a short contact time associated with a high ozone dose was preferable to a long contact time and a low ozone dose.     

The Formation of Filter-Removable Biodegradable Organic Matter During Ozonation

Biodegradable organic matter formed during the ozonation of natural waters was fractionated into rapidly and slowly degradable components based on measurements of biodegradable organic carbon (BDOC). The rapidly degradable fraction (BDOC_rapid) was defined using the specific BDOC reactor incubation time that resulted in biodegradation similar to that in a pilot scale biofilter. Ozone dose was found to increase the formation of BDOC_rapid up to a transferred dose of 1.0 to 1.5 mg O₃/mg DOC. This fraction was insensitive to DOC quantity or character. The formation of BDOC_slow was not sensitive to ozone dose but was sensitive to DOC quantity.