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.     

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.     

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.     

Ozonation at Belle Glade,Florida : A Case History

In October 1984, the city of Belle Glade, FL installed a two-stage ozonation process for the treatment of lake water high in organics (av TOC 30 mg/L; up to 75 mg/L), high in color (av 100 color units; up to 500), and high in THM concentrations, at times nearly 1,000 μ/L. The new treatment process applied 3 mg/L of ozone to the raw water ahead of the flash mix basin, lime softening, alum and polymer coagulation, clarification, recarbonation, and addition of 3 mg/L ozone prior to filtration. Post-chlorination then produced distribution system THM concentrations averaging 124 μg/L. Distribution of THMs shifted from 85% chloroform by the original process to 40% after adoption of ozonation, the balance comprising brominated species (but not bromoform).

In 1987, the treatment process was modified by adding chlorine and ammonia at the outlets of the pre- and intermediate-stages of ozonation and abandoning free chlorination. This has further reduced the distribution system THM levels to 20-30 μg/L. Filtered water turbidity and color have been improved. The use of chloramines after ozonation controls the nuisance aquatic growths in the clarifiers and recarbonation basins (caused by ozonation alone), and produces a combined chlorine residual which can be maintained throughout the distribution system. Periodic use of free chlorine in the distribution system is required to prevent elevated heterotrophic plate counts and the formation of excessive concentrations of nitrite ion due to biological regrowth and nitrification.     

Biological Filtration for Ozone and Chlorine DBP Removal

This paper presents results from a water treatment pilot testing program in Winnipeg, Canada (pop. 650,000) which evaluated a DAF/ozone/deep bed filtration process. As part of the testing program, biological filtration using GAC and anthracite media was assessed for the removal of ozone DBPs and background chlorine DBPs (due to upstream chlorination of the source water). The results were used to evaluate the effectiveness of biological filtration for DBP removal.

High filtration rates were tested in this study. The 2.1m deep filters were run at a hydraulic loading rate (HLR) of 35 m/h with an empty bed contact time (EBCT) of only 3.6 minutes.

The important findings of this work are

?The high-rate biologically active carbon (BAC) filters met the objective of controlling ozone DBPs. These results confirm that high rate, low EBCT filters can provide significant biodegradation. Anthracite biofilters provided significantly less removal of ozone DBPs.

?The high rate BAC filters showed significant reduction of background HAAs. BAC reduced the background HAAs to below the long-term target of 30 μg/L. Anthracite biofilters did not exhibit HAA removal.

?Biological filtration with either media was ineffective for background THM removal. The long-term target of 40 μg/L could not be achieved without GAC adsorption.     

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.     

The Price Of Ozonation In The Paris (France) Suburbs

The purely economic aspects of ozonation have, until now, given rise to surprisingly few publications. Yet they are of ever-growing importance in deciding on the choice of a system, if only because the number of competitive technical solutions available for ozone production has greatly increased.

First of all, an obvious fact must be remembered. Each installation is a special case. It is therefore out of the question to present general results with direct across-the-board applications. On the other hand, it is possible to engineer a general methodology for price calculation and apply it to a few specific examples. As operator of a large number of these facilities, Compagnie Générale des Eaux can present economic results in many, widely different technological economic conditions.

Generally speaking, it can be said that the cost of ozonation is increasingly optimized. This technique, considered a few years ago as a luxury, is now technically and economically ready for incorporation on an equal footing in most treatment trains.     

Sludge Pre-Treatment through Ozone Application: Alternative Sludge Reuse Possibilities for Recirculating Aquaculture System Optimization

Recirculating Aquaculture Systems (RAS) reduce water consumption by efficient filtration to maintain appropriate levels of accumulating compounds and sludge. Sludge is mechanically separated by drum filters and disposed of to the detriment of overall system water budgets. Dissolved nitrogen compounds are reduced via nitrification–denitrification filters, requiring commercial external carbon sources. The reuse of sludge after ozone pre-treatment may represent the next step in RAS optimization. The present study analyzes the content of sludge from RAS and tests ozonation as a pre-treatment for recycling as carbon source. The dissociative effect of ozone and the physicochemical changes due to ozonation lead to a significant increase in soluble carbon availability. Predominantly long-chain fatty acid (FA) (saturated and unsaturated) with 16 and 18 carbon atoms independently of the treatment were found in the profiles. Saturated FA concentrations in solution increased after 20, 40, and 60 min ozonation. The solid content of the sludge was practically unaffected by ozonation in terms of FA profile: only saturated FA slightly increases after 40 min treatment. The implications of these findings for denitrifying bacteria are discussed.

Abbreviations: Recirculating Aquaculture Systems (RAS); Advanced Oxidation Processes (AOPs)     

Ozone Treatment in Cooling Water Systems

Ozone treatment for preventing the biofouling in cooling water systems is investigated.

In the fresh water system, the separating effect of the ozonated water on the microorganisms such as the sphaerotilus and the zoogloea which adhere to the piping and form the slime is recognized. When the ozonated water is supplied intermittently to the piping without stopping the flow of the cooling water, a constant volume of cooling water can be maintained. At the velocity of 1 m/sec, the amount of metal corrosion produced by the ozonated water is reduced on the mild steel, increased on the copper and does not change on the cast iron, when compared with that produced by the water containing no ozone.

In the seawater system, since many substances are oxidized by the ozone, the same treatment as that in the fresh water system cannot be applied. However, if the seawater in the cooling system can be replaced with ozone-containing air intermittently once a week, the adhesion of organisms such as barnacles and mussels to the piping can be prevented without having a bad influence on the other living oceanic organisms.     

New Pilot Plant Studies at the Budapest Waterworks

The quality of water provided by the Budapest Waterworks should comply with the standards prescribed by the European Community. According to these provisions, on one of the major water-producing regions (Csepel Island), rows of wells of 60,000 m³/day yield have been closed recently, and in the immediate future further plants would have been closed because of the high iron and manganese content of the water.

The raw water obtained from 100 different wells will be purified by a water treatment plant of 150,000 m³/day capacity. Considering the high iron content (0.05–0.15 mg/L) and manganese content (0.05–0.2 mg/L), the raw water fails to comply with the requirements of the potable water standard.

Since 1990, over a period of three years, we conducted water purification experiments in several stages. In these, three methods of oxidizing as well as single and double layer open rapid filters were applied to oxidize the manganese (and, to a lesser extent, the water) present in dissolved form, resp., to destroy various living organisms.

In the course of the experiments, it became clear that the chlorine and chlorine + air methods are efficient in case of a small quantity of iron to be oxidized and only 20–25% of the dissolved manganese content could be oxidized.

Neither of the two methods could ensure firm management of microbiological and bacteriological characteristics. The best results were obtained by ozone oxidation, in which case the chemical oxidizing process was almost fully completed and even the chlorine-resistant living organisms could be destroyed.

On the basis of the experiments carried out, the investment program of the water treatment plant was worked out and the conditions of an international tender were compiled whose winner will be commissioned to build up the water works in the time period 1993–1996. One of the main steps of the proposed technology is the ozone treatment.     

Effects Of Ozone As A Biocide In An Experimental Cooling Water System

Experimental work on a laboratory recirculating apparatus, for the simulation of a cooling water system has yielded information on the effectiveness of ozone as a biocide for biofouling control. Biofilms were developed within glass tubes of the simulated cooling water system using filtered mainswater and Pseudomonas fluorescens as the test bacteria. A summary of the results obtained is presented and an interpretation of these results relating to the full-scale application of ozone is provided.

Ozonated water was produced using a contact system specifically designed for these tests by Ozotech Ltd. Ozone residual concentrations in the order of 0.1 mg/L were found to be capable of removing 80-99% of the biofilm in single applications. However, effectiveness of ozone was dependent on morphology, thickness and age of the biofilms. Intermittent application of ozone, using residual concentrations < 0.1 mg/L, was found to be capable of weakening the biofilm, but a minimum period of 3-h was required for effective control.

The fluid velocity was found to affect the rate and amount of biofilm removed. The effects of fluid velocities in the range 0.5-2.5 m/sec were examined. In general, the higher the velocity the greater the initial rate of removal and the percentage of the biofilm removed; this suggested that ozone action was mass transfer dependent.

The effect of ozone on bacterial cell structure was investigated using scanning electron microscopy techniques. Changes in cell structure were revealed after contact with ozone and residuals above 0.4 mg/L were required for 100% kill of bacterial suspensions.

In conclusion, the effectiveness of ozone for full-scale application will vary depending on the morphology of the biofilm, the velocity of the fluid and the ozone dose applied. An ozone dosing regime for commercial application is suggested.