Using Fractionated Natural Organic Matter to Quantitate Organic Byproducts of Ozonation

An improved procedure was used to isolate and fractionate natural organic matter (NOM) in water for subsequent ozonation and disinfection by-product (DBP) and color removal quantisation. Isolated NOM fractions from two different sources, accounting for approximately 50 to 60% of the dissolved organic material and 60 to 75% of the color, were characterized and then ozonated under conditions approximating those encontered during drinking water treatment. The natural waters also were ozonated. Organic DBPs of either health concern or which may contribute to biological instability of finished water were investigated, including aldehydes, oxoacids and low molecular weight carboxylic acids. pH and ozone dosage were the parameters having the greatest effect on DBP formation. On the basis of UV absorbance measurements, the fulvic acid fractions studied taken together accurately represented the natural water and may be the primary sources of precursor material for aldehydes and oxoacid DBPs. However, as yet unidentified NOM fractions contribute significantly to carboxylic acid formation upon ozonation.     

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.     

Influence of Ozonation of Humic and Fulvic Acids on Diuron Adsorption on Activated Carbon

The effect of ozonation on the competitor effect of humic and fulvic acids against diuron in adsorption on activated carbon in drinking water process has been studied. Ozonation treatment allows the removal of herbicides from drinking waters by modification of humic and fulvic acids structures. These latest are responsible for their adsorption variation on activated carbon. An ozone dose similar to that used in industrial pre-ozonation (1.3?mg ozone/l) does not cause significant transformations of humic and fulvic acids which could decrease their competitor effect and increase significantly the adsorption capacity of the activated carbon for a well-adsorbed pesticide like diuron.     

Iron and Manganese Removal with Ozonation in the Presence of Humic Substances

The conditions for the removal of iron and manganese contained in slightly mineralized water, rich in humic substances, were determined in a case where an intermediate oxidation was provided in a conventional potabilization line comprising a coagulationflocculation stage with iron salts.

The experiments were conducted both on a synthetic water, with or without addition of humic substances, and on raw water from the Moulin-Papon dam. While iron was easily removed by simply increasing the pH measurement from 8.2 to 8.5 without intermediate oxidation, ozonation applied to water with a pH of nearly 8.4 did not enable the manganese to be removed with a low ozone dose (about 1 mg/L) unless a significant amount of bicarbonates (120 to 130 mg/L as CaCO₃) were injected prior to the ozonation-filtration stage.

As it removes the manganese from the water, intermediate ozonation also removes the abatement of organics on the filters, and lowers the THM buildup potential.     

Heterogeneous Catalytic Ozonation with Supported Titanium Dioxide in Model and Natural Waters

This paper presents the results obtained with heterogeneous catalytic ozonation in which model and natural waters are ozonated in the presence of supported titanium dioxide (TiC₂) as a solid catalyst. The conditions in preparing the supported catalyst are experimentally optimized. The efficiencies of three catalyst supports (attapulgyte, alumina and silica gel) for organic matter oxidation have been compared. The TiC₂ supported in alumina calcined at 500[ddot]C compacted to granular form with a particle diameter about 2-4 mm is demonstrated to be the best catalyst on the removal total organic carbon (TOC) by ozone.     

Origin and Conditions of Ketoacid Formation During Ozonation of Natural Organic Matter in Water

The batch ozonation of some fractions of aqueous humic substances (humic, fulvic and hydrophilic acids) extracted from natural waters is studied. The reaction leads to oxidation byproducts such as low molecular aldehydes and ketoacids. Formation conditions and origin of some of them (glyoxylic, pyruvic and ketomalonic acids) regarding the extracted fraction of natural organic matter is established.     

Perovskite Catalytic Ozonation of Some Pharmaceutical Compounds in Water

The ozonation of two pharmaceutical compounds: the drug diclofenac (DCF) and the synthetic hormone 17α-ethynylstradiol (EST), has been studied in laboratory prepared water and domestic wastewater in the presence of perovskite catalysts. In ultrapure water, catalysts do not lead to any improvement on the ozonation rates of DCF and EST which supports the fact that both compounds are removed by direct ozonation. TOC removal, on the other hand, is significantly increased in the presence of perovskite catalysts, especially when copper perovskite is used, with TOC removals in the order of 90% after 120 minutes of reaction. In domestic wastewater the results are similar regarding the mechanism of initial pharmaceutical compounds removal, which are due to direct reactions with ozone that, in this case, develop during longer reaction times likely due to the presence of other contaminants. Then, regarding TOC removal in domestic wastewater, negligible differences between non-catalytic and catalytic ozonation are observed during the first approximately 25 minutes of reaction. For higher reaction time, TOC removal is improved only in the case copper perovskite catalyst is used although percentages of TOC removal are comparatively lower than those reached in ultrapure water (they hardly reach 50% TOC removal). Finally, a kinetic study has been carried out and apparent rate constants of the heterogeneous reaction between ozone and TOC on the catalyst surface have been determined.     

Ozonation/Post-Chlorination of Humic Acid: A Model for Predicting Drinking Water Disinfection By-Products

Experiments were performed to evaluate disinfection by-products in model humic acid solutions which were ozonated at three different ozone to carbon levels and then chlorinated. These experiments were conducted in order to help understand whether the ozone/post-chlorination process alters the amount and type of mutagenic by-products formed, from those produced by chlorination of humic acid alone. Disinfection by-products were identified by gas chromatography/mass spectrometry (GC/MS). Samples of clarified and sand-filtered Mississippi River water at a pilotscale drinking water treatment plant in Jefferson Parish, Louisiana, that were ozonated and post-disinfected with chlorine, also were analyzed by GC/MS. A comparison of the by-products in the pilot plant study versus those in our laboratory study showed that similar compounds were produced. The effect of bromide ion in the pilot plant water on by-product formation also is discussed.     

The Oxidation of Manganese and Disinfection By Ozonation in Water Purification Processing

The surface water of a river has been used as the raw water by the Waterworks Bureau of Osaka City. At present, the manganese contained in the raw water is oxidized by breakpoint chlorination and all oxides are removed by coagulation, sedimentation followed by rapid sand filtration, with chlorine being used as the final disinfectant.

Prechlorination was not conducted in the ongoing pilotplant experiment of an advanced water purification process with ozone and granular activated carbon. It is necessary, therefore, to oxidize manganese by the oxidative effect of ozone instead of prechlorination.

It is important for the treatment of manganese to adjust the ozone dosage because manganese is oxidized up to the soluble septavalent state by the surplus ozone. Since ozone does not continue to exist for very long in water, though its disinfecting power is high, final disinfection by chlorine is required.     

Ozonation of Humic Substances: Effects on Molecular Weight Distributions of Organic Carbon and Trihalomethane Formation Potential

Four different sources of humic substances were studied to determine the effects of ozonation on molecular weight-distributions, based on dissolved organic carbon (DOC) and trihalomethane formation potential (THMFP). Solutions of two soil-derived fulvic acids and a one soil-derived humic acid, as well as dissolved organic matter (DOM) associated with a natural water source were studied. Both gel permeation chromatography (GPC) and ultrafiltration (UF) were employed to define apparent molecular weight (AMW). Applied ozone doses ranged from 2.0 to 2.5 mg O₃/mg DOC. Overall samples of untreated and ozonated waters, as well as individual molecular weight fractions, were characterized according to DOC, UV absorbance, and THMFP. Ozonation resulted in a significant disappearance of higher AMW material with a corresponding increase in lower AMW material. Although little overall reduction in DOC concentration was observed, significant overall reductions in UV absorbance and THMFP levels were observed.     

Mineralization of Ibuprofen and Humic Acid through Catalytic Ozonation

Advanced oxidation methods are used to remove traces of pharmaceuticals from aquatic environments. The application of a catalyst improves the total organic carbon removal during ozonation of pharmaceuticals in water. The aim of this study was to use MnO₂-CuO/ γ-Al₂O₃ catalyst for ozonation of ibuprofen (5 mgL^?1) and evaluate the effect of the presence of humic acid in the removal process. The presence of the catalyst increased the mineralization percentage of ibuprofen from 27% for noncatalytic ozonation to 55% in the presence of catalyst. The presence of humic acid increased noncatalytic mineralization by 10%. The reusability and stability of the catalyst, and its ability to adsorb reaction by-products were demonstrated.     

Effects Of Catalysts During Ozonation Of Salicylic Acid,Peptides And Humic Substances In Aqueous Solution

The oxidation of two model molecules (salicylic acid and a peptide) and humic substances in aqueous solution was studied using ozone in the presence of various catalysts. Experiments were performed in reactors operated either in batch (TOC_o = 2.5 mg C.L^?1) or in semi-continuous flow mode (TOC_o = 42 mg C.L^?1).     

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.     

Application of DNPH Derivatization with LC/MS to the Identification of Polar Carbonyl Disinfection Byproducts in Drinking Water

A qualitative method using 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by analysis with liquid chromatography (LC)/negative ion-electrospray mass spectrometry (MS) was developed for analyzing and identifying highly polar aldehydes and ketones in ozonated drinking water. Using this method, aldehydes could be easily distinguished from ketones by differences in their mass spectra and chromatographic behavior. Results for many polar-substituted aldehyde and ketone standards are presented, as well as the identification of polar disinfection by-products (DBPs) in ozonated drinking water from full-scale plants and laboratory-scale ozonation of humic acid. One polar DBP identified has not been previously reported. This method could also potentially be used as a tool to identify carbonyl-containing DBPs from disinfectants other than ozone. However, the detection limits for the DNPH-LC/MS method are not as low as for the pentafluorobenzylhydroxylamine (PFBHA)-gas chromatography (GC)/MS method (LC/MS is typically not as sensitive as GC/MS). Therefore, it is not recommended that this method replace the PFBHA-GC/MS method, but be used as a supplement to enable the identification of highly polar carbonyl-containing DBPs that would not be possible by GC/MS.     

Catalytic Ozonation of Gasoline Compounds in Model and Natural Water in the Presence of Perfluorinated Alumina Bonded Phases

Gasoline compounds are one of the most widespread causes of soil and groundwater contamination. Their degradation in model and natural waters due to catalytic ozonation in the presence of perfluorooctylalumina (PFOA) is presented and discussed in this paper. The results obtained clearly indicate that the PFOA/O₃ system is effective mainly for ether (MTBE and ETBE) removal from both model and natural water. The catalytic activity of PFOA is not so significant in the case of BTEX ozonation. An investigation into by-product formation has shown that the concentration of both carboxylic acids (mainly oxalic acid) and carbonyl compounds (mainly acetone) increases after catalytic ozonation when compared with ozonation alone. A decrease of formic acid and formaldehyde takes place after the PFOA/O₃ system as opposed to the usage of ozonation alone.     

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.     

The Influence of H2O2 in Ozonation Treatment: Experience of the Water Supply Service of Florence,Italy

This paper reports on the use of ozone in the Water Supply Service of Florence (Italy). The addition of hydrogen peroxide at the end of ozonation treatment has proved particularly efficient for controlling bromates and brominated organic byproducts. Significant differences regarding the formation of oxygenated organic compounds were not observed.     

Removal of Atrazine Through Ozonation in the Presence of Humic Substances

The presence of pesticides in water sources and their removal by treatment processes is of particular interest currently to water companies and research scientists. Although operators and scientists are debating whether the related standards and legislation are too stringent, the current European Drinking Water Directive stipulates a maximum contaminant level (MCL) of 0.1 μg/L for an individual pesticide. Atrazine is amongst the most frequently identified pesticides in water supply sources. Since conventional treatment processes (chlorination, coagulation and filtration) are unable to reduce this micropollutant to an acceptable concentration, two advanced technologies are being investigated extensively; namely, adsorption onto activated carbon, and ozonation, particularly ozone combined with hydrogen peroxide. As for ozonation, several authors (Glaze et al., 1987; McGuire and Gaston, 1988; Terashima, 1988; Ferguson et al., 1991) have reported that the removal of refractory organics (e.g., 2-methyl isoborneol – MIB and geosmin) by ozone appears to be more effective in natural waters than in pure water solution; this was attributed to the action of natural organic material in water (such as humic substances) which promotes the radical reactions of ozone. In other more fundamental studies (Staehelin and Hoigné, 1985; Xiong and Legube, 1991), humic substances were speculated to be involved in radical decomposition of ozone in solution.     

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.     

Effect of Ozonation on the Chlorine Demand of a Treated Surface Water and Some Macromolecular Compounds

The study described in this paper was conducted to examine the effects of ozonation and ozone-GAC filtration treatment steps on chlorine consumption of the Seine river water treated in the Choisy-le-Roi drinking water works. Ozone-GAC combined treatment was found to significantly reduce both the initial chlorine demand and the long-term chlorine demand of waters, excepting for waters sampled during cold months of the year. The removal of the chlorine demand potential by ozonation alone was found to be limited for the studied waters and for solutions of macromolecular compounds even in the presence of carbonate species. Ozonation carried out in the absence of bicarbonate ion was found to increase reactive sites with chlorine treatment of an aquatic fulvic extracted from the Seine river water.