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.     

Removal of Aromatic Nitro Compounds from Water by Ozonation

Experimental studies were carried out on the removal of five species of aromatic nitro hydrocarbons by ozonation. Ultraviolet spectrograms with distinct absorption peaks were plotted for each of them. It has been found that the absorbances of aqueous solutions containing the single compounds mentioned above increase to different extents at the wave lengths ranging from 200 to 230 nanometers with increase of ozone dosages. This is ascribed to the nitrite ions splitting out of the benzene rings and being further oxidized to nitrate ions by ozonation.

It has been indicated that the removal of the five species of aromatic nitro compounds by ozonation can well be expressed mathematically by first order reaction equations. Besides, the reaction constants and half-life periods for various species of the tested nitro compounds were calculated at different temperatures and pH.

An ozonation effect index (OI) was developed in the study to express the degree of degradation of substrates by ozonation, by means of which the five aromatic nitro hydrocarbons were compared with each other and finally ranked in the following order from greatest to smallest degrees of degradation:

p-nitroaniline > nitrobenzene > p-dinitrobenzene > p-nitrotoluene > m-dinitrobenzene

It has also found that the CODm/M ratio increases with ozone doses. This means that some easily degradable intermediates are produced, and increase in concentration with increase of ozone dose in the ozonation process.

The mechanisms of removing the five aromatic nitro hydrocarbons are discussed from the viewpoint of orienting effects of substituent groups on the aromatic rings.     

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.     

Comparison of Ozone and Hydroxyl Radical-Induced Oxidation of Chlorinated Hydrocarbons in Water

The efficiency of ozonation and advanced oxidation processes such as ozone/UV, ozone/H₂O₂ and H₂O₂/UV was assessed for chlorinated hydrocarbons using a closed batch-type system. 1,1-Dichloropropene (DCPE), trichloroethylene (TCE), 1-chloropentane (CPA), and 1,2-dichloroethane (DCA) were used as model compounds.

The direct reaction between substrates and ozone predominated at lower pH, which resulted in the efficient oxidation of the olefin, DCPE. At higher pH, ozonation resulted in more efficient oxidation of the chlorinated alkanes, with a corresponding decrease in the efficiency of DCPE oxidation. Consistent results were observed for ozone/H₂O₂ and ozone/UV treatment. Due to slow UV-induced decomposition of H₂O₂, the process using H₂O₂/UV (254 nm) resulted in very slow oxidation of all four compounds.

The total ozone requirement to achieve a given degree of elimination (to 37% of the original concentration), δ0.37, was used to assess the combined effects of the direct and indirect reactions for different types of waters.     

Effect of Preozonation on Flux and Water Quality in Ozonation-Ultrafiltration Hybrid System for Water Treatment

The effect of ozonation on membrane flux and water quality was investigated in an ozonation ultrafiltration (UF) hybrid system. Crossflow UF was performed in total recycle mode to study the effect of ozonation on membrane fouling and disinfection by-product formation potentials of organics. Total organic carbon (TOC), UV absorbance at 254 ran (UV254) and trihalomethane formation potential (THMFP) were measured as water quality parameters.

The effect of ozonation on membrane flux was found to be largely dependent on raw water quality as well as ozone dose. In case of upstream water (A), preozonation achieved significant flux enhancement regardless of ozone dose. Whereas, for the downstream water (B), the steady state flux was increased or decreased depending on ozone dose.

The analysis based on the resistance-in-series model provided the mechanistic interpretation on the membrane flux variation. Ozonation in an ozone-ultrafiltration system always brought about a decrease in cake resistance (R_c) and an increase in fouling resistance (Rf). Based on the measurement of particle size distribution and zeta potential, the reduction in cake resistance through ozonation was attributed to an increase in particle size due to “ozone-induced particle destabilization”. However, the increase in the fouling resistance seems to be caused partly by the microbial characteristics of raw water.

Although there was little effect on TOC, ozone-UF treatment could get much higher removal of UV 254, THMFP (lday) and THMPF/TOC ratio than UF treatment alone.     

Effect of Ozone Dosage for Removal of Model Compounds by Ozone/GAC Treatment

This research employed batch ozonation and GAC (granular activated carbon) column to investigate the effect of preozonation dosage on the subsequent GAC adsorption, in terms of the adsorption capabilities for small and large molecules.

For large target compounds like humic acid, the adsorption efficiency was improved with higher ozone dosages, whereas the combined effect of ozonation coupling with GAC for small model compounds seems to be negative. In addition, there is a selective adsorption between the chlorinated disinfection by-product (DBP) precursors and other non-precursors, and most of the non-precursors are less adsorbable than the precursors.     

Modelling Industrial Wastewater Ozonation In Bubble Contactors. 2. Scale-up From Bench To Pilot Plant

A kinetic model constituted by ozone mol balance equations both in the gas and in the water phases and a total mole balance equation has been applied to predict concentrations of dissolved ozone, C_o3, ozone partial pressure at the reactor outlet, P_(o3)0, and remaining chemical oxygen demand, COD, for the ozonation of two industrial wastewaters released from distillery and tomato processing plants.

Kinetic equations for ozone absorption rate present in the model were derived from the application of film theory to an irreversible gas-liquid reaction. Parameters involved in the model, reaction rate and mass transfer coefficients, Henry's law constant, etc., were estimated from bench-scale experiments. The model was applied to ozonation in bubble contactors of height/diameter ratio equal to that of the bench scale contactor and to a pilot plant bubble column of a height/diameter ratio about 3.6 times higher.     

First Year Operation Report of the Corona Discharge Ozone Swimming Pool Water Treatment Systems at the Peck Aquatic Facility,Milwaukee, Wisconsin

The two corona discharge ozone swimming pool water treatment systems installed in the Peck Aquatic Center in Milwaukee, WI now have been in continuous operation since September, 1987. The two pools are part of the Karl Jewish Campus Facility of the Harold and Judy Sampson Campus of the Milwaukee Jewish Community Center.

The operation of these water treatment systems has shown that safe and high quality pool water is obtained reliably and economically. One pool (Main Pool) is of Olympic size, the other (Learner pool) is designed especially for use by children. Both pools utilize a full corona discharge ozone water treatment system. They were the first ozone systems in the U.S. to be built for public pools using the process of ozonation, flocculation, filtration, ozone removal and residual chlorination.

An extensive testing program was initiated in cooperation with the Wisconsin Department of Health. The bacteriological water quality from these swimming pools was in compliance with Wisconsin State Health Regulations and the German DIN Standard 19,643.

The first year of operation of the Peck Aquatic Center has shown that the corona discharge ozone pool water treatment process can:

1) Operate reliably in a public swimming pool environment without the need for highly or special operator qualifications.

2) Produce continuously bacteria- and virus-free pool water without the harmful and unpleasant effects of chlorine.

3) Creates a user constituency group praising and promoting the use of “minimal chlorine swimming” in the community.     

Optimization Of Ozone Plants For Water Works In Switzerland

The disadvantage that chlorine as processing agent in the treatment of surface waters can lead to undesirable production of chlorinated hydrocarbon products, provided the impulse to involvement in alternate means of oxidation. This inevitably led the way to the means of oxidation used the most intensively in water treatment - ozone.

Extensive development work has been performed to optimize the dosage of ozone for water treatment. Potential users are kept informed on this technology through published data. Theory, however, is only one side of the problem, practical application quite another. Here technicians and engineers have been required to integrate oxidation and disinfection with ozone, into the technology for water treatment and to make this economic.

In Switzerland since the 1950s, more than 40 waterworks have been converted to ozone. The development and the experience that has been collected since the introduction of this technique is the subject of this paper, primarily in regard to cost development and cost economy through innovative engineering services for development, engineering and project execution.     

Removal Of Pesticides By Use Of Ozone Or Hydrogen Peroxide/Ozone

This article deals with the efficiency of an ozonation step in drinking water treatment plants remove pesticides. These tests are carried out with a laboratory technique, the “OZOTEST” method, which simulates operating conditions on site and allows a complete oxidation assessment.

Efficiency of the two oxidant systems – ozone and ozone coupled with hydrogen peroxide – is evaluated for 11 pesticides commonly analyzed in control laboratories. Comparison of the two systems is made in terms of pesticide removal, but also in terms of ozone consumption. Matrix effects and contact time are also taken into account, and an order of reactivity for each system considered is suggested.     

Simulation Of Ozone Transfer In Water. Comparison With A Pilot Unit

A computer simulation of a bubble column is established to determine the residual ozone concentration in the air and the dissolved ozone residual in the water. This study is aimed to improve the control of ozonation systems, both technically and economically.

The program is based on mass balances along the contact column, which take into account the ozone consumption due to both the self-decomposition and the reactions with organic compounds contained in the water. The experimental measurements allow quantification of the ozone concentration in the air at the inlet and outlet of the pilot unit, as well as the dissolved ozone concentration at different heights along the column. A relation between the transfer coefficient, k_La, and the superficial velocity of the ozonated air is established. It is specific to the diffusion characteristics of the pilot unit. The k_La then is reintroduced in the program.

The calculated and the measured values are shown to be similar regarding the transfer yields, the dissolved ozone concentrations at the pilot unit outlet and the profiles of dissolved ozone concentrations along the contact column. Using the program, the influence of the most important parameters of ozonation on the transfer (treatment rates, initial ozone concentration in the air, pH and organic content of the water, k_La values) have been simulated.     

Application of Oxidation by a Combined Ozone/Ultraviolet Radiation System to the Treatment of Natural Water

When treating natural water, the simultaneous use of ozone and UV rays can lead to high level oxidation of the ozone–refractory organics. The main parameters affecting the efficiency of the O₃/UV system are: the ozonation rate, the average UV radiation intensity, the pH measurement, alkalinity, and the type of compound to be oxidized.

In optimum Ou/UV system application conditions, the abatement of COD in water from the Seine river is never above 30%. On the other hand, TOC removal is increased in weakly carbonated pond water loaded with humic matter. The O₃/UV system also ensures oxidation of saturated volatile organic halogens, with the exception of carbon tetrachloride.     

Safety Problems in Ozonation Plants

In water treatment plants equipped with large–scale ozonation facilities, specific safety measures must be constantly reviewed and tested. Safety of employees : in high concentrations, ozone becomes a poisonous gas. This requires adequate means for detection of ozone in traces in the ambient air. ventilation and destruction. individual protection Safety of plant and equipment : ozonation has become an essential phase in the treatment process and ozonators must be fitted with safety devices for the detection and rapid control of hazardous conditions.

Experience shows that the measures taken to ensure the safety of employees also improve safety for plant and equipment, and vice versa. The solutions applied demand extra effort at the design stage of the plant, but in return, they result in notable improvements in operating conditions and costs.     

UV-induced Decomposition of Ozone and Hydrogen Peroxide in the Aqueous Phase at pH 2–7

The photolysis of ozone and formation of hydrogen peroxide were investigated in solution of pH 2–7, in a 200 cm³ photoreactor in the incident photon flow range 9.6 x 10^?8 - 4.2 x 10^?7 einstein s^?1. The quantum yield of the primary photochemical reactions was measured in a direct way by suppressing the secondary radical reactions. The determined quantum yields of the photo-decompositions of ozone and hydrogen peroxide were 0.42 ± 0.042 ± 0.04 and 0.49 ± 0.04, respectively.

A correct mathematical treatment is given for calculation of the light absorption of the individual components of a multi-absorbent reaction mixture.

On the basis of the literature data and die present results, a probable chemical and reaction kinetic model was proposed to characterize the investigated reaction systems. Reaction kinetic simulations demonstrated that the model predicts a good fit to the measured data with the preferred literature rate constants, except that for the HO₃ radical decomposition reaction. A reasonable reduction of this rate coefficient value is in accordance with the latest published results.     

Ozonation of Sulfur-Containing Aliphatic Compounds in Aqueous Solution. I

In view of the possible reaction of ozone with sulfur containing natural and anthropogenic compounds, the oxidation products of sulfur-containing aliphatic model compounds in pure water in dependence on pH value were investigated.

In the first part, as a model compound for thioether, thiodiglycolic acid was investigated. The rate of elimination is independent of pH-value. At pH 3 as primary product thionyldiglycolic acid is formed, which undergoes further oxidation, but very slowly, to sulfonediacetic acid, which is very stable against ozone attack at pH 3. At pH 7 and higher, however, thionyldiglycolic acid is oxidized faster to sulfonediacetic acid, and this compound is oxidized to sulfoacetic acid, oxalic acid, glyoxylic acid, sulfateion, and CO₂ after longer reaction times. In all cases, sulfite as an inorganic intermediate product could not be identified. Also the intermediate products in pure solutions are ozonized. The mass balances show that 90 to 95% of the oxidation products could be identified. Based on these results, reaction schemes are discussed.     

Ozone for Removal of Acute Toxicity from Logyard Run-Off

Stormwater run-off from wood handling facilities is garnering increasing attention from environmental regulators. In an effort to develop treatment methods to deal with the problem of toxic run-off from logyard and dryland sorts, we are currently investigating the use of ozone.

Samples of logyard run-off were obtained from two British Columbia coastal sawmills. Ranges obtained for measured parameters of these samples were as follows: COD 2400-8700 mg/L, tannins and lignins 160-2500 mg/L, BOD 190-1900 mg/L, acute (Microtox) toxicity EC₅₀ 2%–27% v/v. Centrifuged samples were treated with ozone doses up to approximately 0.5 mg ozone/mg COD in a lab-scale reactor.

Ozonation was found to significantly reduce toxicity (80%-90%), tannin and lignin (TL) (90%-95%) and dehydroabietic acid (DHA) (95%-100%) levels. There were moderate reductions in COD (30-35%) and BOD (15%-25%). At slightly acidic to neutral pH, pH had no effect on the rate of COD oxidation; TL and toxicity removal were slightly improved in neutral solutions compared to acidic ones, while DHA removal significantly improved     

Determination of Rational Conditions of Preliminary Ozonation of Nonionic Polyethoxylated Surfactants before Biosorption

The influence of preliminary oxidation of nonionic surfactants solutions on the biosorption efficiency of activated carbon was investigated. The Gibbs free energy of adsorption (?ΔG^o _a) of oxidation products from water on an activated carbon was used as a parameter of the bacterial resistance of oxidation products adsorption. It was established for nonionic surfactants, that ozonation essentially raised the contents of nonionic surfactant homologues with a low degree of ethoxylation. It leads to the increase in the Gibbs free energy of oxidation products adsorption and to inhibition of biodegradation process.

It was shown that the efficiency of biosorption process after preliminary ozonation was 2–3 times lower than without preliminary treatment that correlated with changes of the free energy of adsorption.     

Reactivity Studies In The Ozonolysis Of Pollutants Using A Perforated Spinning Disc Reactor To Enhance Mass Transfer

A perforated spinning disc ozone contactor is described with reference to its use as an absorber with simultaneous chemical reaction.

Greatly enhanced mass transfer coefficients k_L are measured whilst simultaneously maintaining low ozone loss. Comparisons of k_L and volumetric coefficient, k_L a values, are made with more conventional packed or bubble columns.

Acetic acid, 2-propanol and 4-nitrophenol, representing a wide reactivity range, are used to elucidate the applicability of rotating contactors in effluent treatment. It has been possible to study the effects of surface activity on mass transfer with subsequent reaction and to generate design data for the next generation of rotating contactors.     

Modelling Industrial Wastewater Ozonation In Bubble Contactors. 1. Rate Coefficient Determination

A study of the ozonation of distillery and tomato wastewaters was carried out in a small bubble contactor in order to obtain kinetic data for scaling-up. Thus, several parameters, such as chemical oxygen demand (COD), 254 nm absorbance (A₂₅₄) and organic carbon content (OC), were followed during ozonation at different experimental conditions.

For distillery wastewaters all parameters investigated have the highest decreases during the first minutes of ozonation, A₂₅₄ showing the highest disappearance rates. Thus, during the first fifteen minutes of ozonation an important decrease of the 254 nm absorbance (? 75%) was observed. At further reaction times values of all parameters studied decrease slowly, eventually reaching a plateau value. During approximately the first two hours of reaction, dissolved ozone was never found, which suggested that fast or moderate gas-liquid reactions took place in the wastewaters.     

Advantages of Preozonation in the Upgrading of the Mont Valérien Plant in France

The Mont Valérien plant supplies water to the western suburbs of Paris. Raw water comes from the River Seine downstream from the city. The old plant comprised two treatment lines: a slow sand filtration line built 80 years ago and a rapid settling and filtration line built in 1960. The process for the upgraded plant was determined after an in-depth study including industrial-scale experiments and laboratory tests.

The new treatment line includes the following: preozonation, oagulationflocculation and settling in a sludge-blanket type settling tank (PULSATOR), rapid gravity sand filtration, ozonation, and granular activated carbon filtration.

Results from laboratory tests used for the design are presented: ozonation rate, advantages for the quality of the treated water, expected reagejit savings, etc.