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.     

Interactions Between Ozone,Halogens and Organic Compounds

During drinking-water treatment, ozone used as a preoxidant and chlorine required for final disinfection, lead to competing chemical reactions, in the case of raw water containing both organic compounds and inorganic salts (such as bromides and ammonia).

The study of the interactions between those reactants has been made according to the following main topics :

As for THM formation, experiments conducted on simple organic compounds or on natural fulvic acids show important decreases in THM or TCAA formation after ozonation. It may be noticed, however, that the ozonation of surface waters may induce the formation of haloform precursors, usually with a low level of reactivity.

In water supplies containing bromide ions, oxidation of the latter through hypobromous acid may take place during the ozonation stage. Failing preozonation treatment, hypobromous acid is generated very rapidly during chlorination, thus inducing the formation of chloro- brominated organic compounds.

During the ozonation of fulvic acid solutions, the presence of small amounts of bicarbonate was found to improve precursor removal significantly.

It can be concluded that the partial analogy of the action of ozone or chlorine on aromatic structures, whether simple or complex (such as humic and fulvic acids), seems to indicate that the consequence of preozonation is the destruction, at least in part, of the most reactive sites for THM production, thus leading to a decrease of the volatile organochlorinated compounds formed during the post-chlorination. However, some ozonation products of natural waters are THM precursors, though of low reactivity. Then, in the presence of bromide ions, the formation of volatile organobrominated compounds may be observed during ozonation.     

Significance of Acoustic and Hydrodynamic Cavitations in Enhancing Ozone Mass Transfer

Assessment of both acoustic and hydrodynamic cavitations for intensifying ozone mass transfer was conducted simultaneously. Four process schemes were arranged to evaluate the effect of application of each kind of cavitation as well as both of them, on the ozone mass transfer process. All processes were conducted at pH of 3 to avoid ozone natural self-decomposition initiated by hydroxide ions (OH^?). The chemical and mechanical effects of cavitation were distinguished by using radical scavengers to suppress radical formation. The result showed that hydrodynamic and acoustic cavitations enhanced ozone mass transfer synergistically. The enhancement obtained from the acoustic cavitation was higher than that obtained from the hydrodynamic cavitation, and the chemical effects of cavitation were much significant than that of mechanical effects. The enhancement obtained due to chemical effects of cavitation was about twice the enhancement obtained due to mechanical effects when only one type of cavitation was combined with ozonation. Combination of both type of cavitation and ozonation gave the enhancement obtained due to chemical effect of 3.68 times that obtained due to mechanical effects.     

Influence of Preozonation on the Formation of Chlorination Disinfection By-products – A Case Study: The Úzquiza Reservoir Water

The influence of preozonation on the formation of chlorination disinfection by-products (DBPs) is studied for three different types of water: a natural water from the Úzquiza Reservoir (Burgos, Spain), synthetics waters prepared using natural fulvic and humic acids extracted from the Úzquiza Reservoir and a synthetic water prepared using a commercially supplied humic acid. The main factors intervening in this process have been reviewed: the delay time between ozonation and chlorination, the ozone reaction pathway, the type of NOM, the applied ozone dose and the presence of bromide ion. Preozonation decreases trihalomethane formation potential (THMFP) for both humic and fulvic acids, being this effect more significant for the humic acids. The molecular pathway of ozone seems to be more selective than the radical pathway for THMFP removal from humic acids. Ion bromide content of the raw water greatly influences the effect of preozonation on THMFP. The influence of preozonation on the formation of some minority DBPs has been studied too.     

Manganese‐catalysed ozonation of glyoxalic acid in aqueous solutions

Manganese‐catalysed ozonation of glyoxalic acid in aqueous solutions has been investigated in the pH range 2.0–4.0. The addition of manganese ions (Mn(II) or Mn(IV)) to a glyoxalic acid–ozone system allows the substrate to be oxidized through a mechanism different from that reported for uncatalysed ozonation, as underlined by the formation of methanoic acid. The presence of solid MnO₂ results in a further increase in the system reactivity. High levels of mineralization are generally achieved during glyoxalic acid‐catalysed ozonation. © 2000 Society of Chemical Industry     

Effects of Ozonation on Molecular Weight Distribution of Humic Substances and Coagulation Processes – A Case Study: The Úzquiza Reservoir Water

In this article the influence of preozonation on the effectiveness of NOM removal via coagulation processes will be studied (focusing on the influence of the calcium hardness) as well as changes in MW (molecular weight) distribution of humic substances caused by ozonation. Additionally, THMFP removal in both ozonation and preozonation-coagulation processes is assessed. Three different types of water have been used in this study: a natural water from the Úzquiza Reservoir (Burgos, Spain), a synthetic water prepared using natural fulvic acids extracted from the Úzquiza Reservoir and a synthetic water prepared using a commercially supplied humic acid. Molecular weights of humic substances were determined using high-performance size exclusion chromatography (HPSEC); average molecular weights calculated for the unozonated humic substances are 4500 Da for the commercial humic acids and 1000 Da for the natural fulvic acids extracted from the Úzquiza Reservoir. Preozonation shifted the molecular weight distribution of humic substances (both humic and fulvic acids) towards lower average molecular weight values. For the natural water from the Úzquiza Reservoir (with low levels of calcium hardness and hydrophobic fraction (humic substances) being the main fraction of NOM), preozonation has a negative effect on the effectiveness of the coagulation process for NOM removal: the percentages of TOC removal via coagulation decrease with increasing ozone dosage; the maximum TOC removal (33%) is achieved for the unozonated water. Also for this water, ozonation reduced 5–25% of THMFP with ozone doses varying from 0.25 to 2.5 mg O₃/L. A preferential THMFP removal, that is to say, higher reduction in THMFP (43%) relative to TOC (28%) is achieved by the coagulation-flocculation process; this also occurs when preozonation is used, independently of ozone dosage.     

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.     

Ozonation of Animal Wastes Containing Oxytetracycline

The efficiency of ozonation on the degradation of oxytetracycline, a veterinary antibiotic, has been investigated in both cow manure and synthetic animal feeding operation wastewater at varying experimental conditions. With a rapid degradation of antibiotic in synthetic wastewater, ozonation improved its biodegradability and eliminated bacterial toxicity caused by oxytetracycline. The degradation rate of oxytetracycline depended on pH and applied ozone dose, but not initial antibiotic concentration in wastewater. In the case of manure treatment, ozonation efficiency in terms of oxytetracycline degradation was negatively affected by moisture and antibiotic content of manure. The degradation rate of oxytetracycline in manure slowed down upon the extension of treatment time since ozone could not react with strongly adsorbed antibiotic on manure. Increase in humic and fulvic acid carbon and mineral nitrogen content was an indicator for the improvement of fertilizing value of manure by ozonation.     

The Effect of Ozonation on the Removal of Organics by Coagulation – Flocculation

We present here some works which take place in the particular framework of the study of drinking water treatment of reservoir waters which contain high concentrations of organics, mainly humic substances. Previous studies on coagulation of fulvic acid solutions have proved that the optimal removal of organic matter was reached at acidic pH with 2 mg of ferricion per mg or organic carbon (summarized in this paper). The main question in this study is to know what is the impact of preozonation on the removal of organics by iron (III) coagulation.

The study of the behavior of organics, in terms of UV-absorbance and TOC measurements was made on three aquatic fulvic acids and on two raw waters. The experiments carried out with fulvic acids showed that preozonation (at 0.5 mg O₃/mg C) of fulvic acid appeared to have shifted the region of the optimal DOC removal towards the higher coagulant dose. Furthermore, increasing ozone doses led to a slight decreasing of coagulation efficiency at constant coagulant dose. With two raw waters, preozonation at low ozone doses (0.2 mg 0₃/mg C) was found to improve very slightly the elimination of organic matter, while high ozone doses (0.9 mg O₃/mg C) led to a disturbance of TOC elimination by iron coagulation.     

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.     

2，4-二氯苯氧乙酸臭氧化过程中过氧化氢的生成

引言2,4-二氯苯氧乙酸(2,4-D,又名2,4-滴)是一种广泛使用的除草剂[1],应用历史较长,是我国主要的除草剂品种之一,用量也比较大。2,4-D属于苯氧羧酸类除草剂的一种,可有效去除阔叶杂草,目前仍广泛用于农作物除草和草坪养护[2]。2,4-D的水溶性较高,挥发性较低,在自然界中难以生物     

Treatment of Water Contaminated with Chlorinated Organic Herbicide 2,4-D by an Ozone/Gamma Process

Radiation-induced degradation of 50 ppm 2,4-dichlorophenoxyacetic acid (2,4-D) was investigated in different ozonation times. Co-60 gamma-source was used as a gamma-source with a dose rate of 0.07 kGy/h. Ozonized samples were irradiated for the 0.2 kGy dose. It is observed that irradiation enhances the degradation of 2,4-D with ozone. The amount of passed ozone from samples is between 0.0695 g/L and 8.33 g/L with a flow rate of ozone at 0.078 L/min (10 g/h), from 10 s to 1200 s with the ozone generator. Aliphatic acids and chloride were determined with ion chromatography. Formaldehyde, dissolved oxygen, pH and total acidity were also measured. Both species and amounts of radiolytic intermediates were determined. 2,4-dichloro phenol (2,4-DCP) is one of the toxic intermediates of 2,4-D observed with GC/MS and it decomposes at further ozonation times. It is observed that combination of ozone/gamma irradiation is more effective for degradation of 2,4-D and its intermediate 2,4-DCP. Chloride ions are observed as completely released with combined processes at lower ozonation times although nearly 98% are released with 20 min' ozonation. Intermediate 2,4-DCP decomposes at earlier ozonation times than 2,4-D.     

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.     

促传剂强化臭氧氧化对硝基酚的研究

研究了传质促进剂（促传剂）对臭氧降解水中对硝基酚的影响，筛选出了两种效果较好的促进剂。实验测定了臭氧在鼓泡反应塔中的传质系数以及添加促传剂后传质系数增大的倍数。还测定了添加促传剂后酚溶液表面张力的变化，并初步探讨了促传剂的作用机理。     

Impact of chemical oxidation on biological treatment of a primary municipal wastewater. 1. Effects on cod and biodegradability

Municipal wastewaters taken from a primary sedimentation tank were subjected to different chemical oxidation processes (ozonation or UV radiation alone or combined with hydrogen peroxide) to observe the evolution of COD and BOD/COD ratios. Ozonation of wastewater led to different increases of COD level reduction depending on pH and carbonate‐bicarbonate ion concentrations. Direct photolysis or hydrogen peroxide alone were found to be inappropriate technologies. On the other hand, advanced chemical oxidation, that is, oxidation with ozone or UV radiation combined with hydrogen peroxide, increased COD level reduction only when wastewater was previously decarbonated. Thus, elimination of carbonate‐bicarbonate ions, increase of pH and addition of hydrogen peroxide (10^‐3 M) yield increases COD level reduction rates. Finally, preozonation also allows improvement of wastewater biodegradability.     

Experimental Investigation on the Microbial Inactivation of Domestic Well Drinking Water using Ozone under Different Treatment Conditions

The effect of ozonation on the microbial activities of domestic well drinking water was investigated, and the influence of the treatment conditions such as pH, temperature, ozone dose, and contact time was elucidated by comparing removal efficiencies. The results revealed that the disinfection of the microorganisms was related to an increase in contact time and thereby increases in Ct values with ozone. Higher ozone doses led to a large amount of microbial inactivation. The addition of hydroxyl and hydronium ions contributed greatly to the destruction of any microorganism in both acidic and basic mediums, achieving 25–88% efficiencies.     

Soil Fulvic Acid Degradation By Ozone In Aqueous Medium

Armadale Armadale soil fulvic acid (SFA) was found to contain several loosely bound organic impurities which could be removed by ethyl acetate extraction. The ozonation of purified Armadale SFA at a variety of dosages was characterized by monitoring the UV absorbance, weight loss, pH changes, total acidity, molecular weight and elemental composition. SFA could only be partially degraded even under ozone dosages as high as SFA/O₃ (w/w) of 1:6. At high ozone dosages (SFA/O3 1:6) mostly aliphatic compounds rich in oxygen were produced, whereas at low ozone dosages (SFA/O₃ < 1:0.5) mainly benzene polycarboxylic acids and polyhydroxy benzene polycarboxylic acids were found. The solid material bisolated from the chlorination (0.5 mg/L residual level) of residues from the ozonation (SFA/O₃ 1:0.2 to 1:0.5) of Contech SFA did not contain any chlorinated products.     

Formation of oxygen structures by ozonation of carbonaceous materials prepared from cherry stones: II. Kinetic study

In this second part, the kinetics of the ozonation process of a char prepared from cherry stones (CS) is investigated. The char was obtained by heat treatment of CS at 600°C for 2 h in nitrogen. The effects of reaction time, partial pressure of ozone, and mass transport phenomena on the formation of oxygen complexes are studied. The surface chemistry of the samples was examined by FT-IR spectroscopy and the elemental chemical analysis was also determined for some samples. Results showed that the ozonation of the char led to oxygen chemisorption and to carbon gasification. The amount of oxygen complexes formed in the chemisorption stage (i.e., OH groups, CO structures, and ether structures) was found to be very sensitive to the increase in the ozonation time. The type of oxygen complexes was also time dependent. Ozonated products with relatively high concentrations of CO groups and ether structures were prepared by applying high ozone doses, whereas the formation of OH groups was favored at low ozone contents. The particle size did not influence the surface chemistry of the ozonated products. Only when the gas flow rate was lower than 40 l h⁻¹, restrictions to ozone mass transport developed. For kinetics of the char ozonation process, a mechanism based on the Langmuir-Hinselwood adsorption-desorption model was proposed, and the intrinsic reaction rates were calculated as a function of ozonation temperature. The activation energy for the ozonation stage of the char was equal to 41.6 kJ mol⁻¹.     

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.     

Characterization of Natural Water for Potential to Oxidize Organic Pollutants with Ozone

A laboratory study has been designed to investigate the decomposition of ozone in natural water and to determine its potential to produce hydroxyl free radicals for the oxidation of micropollutants during the ozonation process of drinking water. This report describes the first data obtained using a continuous flow reactor capable of observing reactions with relatively short time scales (Q = 34 mL/min; 1.4 < t_c < 27 sec). Rates of ozone decay were studied in fulvic acid solution in the presence, or in the absence of radical scavenger (tert-butyl alcohol) or of promoter of ozone decomposition (formic acid), and a micropollutant of interest (tetrachloroethylene). Also, three natural waters were studied, illustrating that OH radical formation depends on chemical composition of the waters.