FullOzoneReport Aclarus

Ozone Reactions with Common Water Quality Parameter
900 Major Bennett Dr.

Peterborough, ON K9J 6X6
t. 888-638-4420 f. 888-371-6455
e. info@Aclarus.ca
i. www.Aclarus.ca
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Table of Contents
Ozone Reactions with Common Water Quality Parameters

Introduction....................................................................................................…..... 1
Fundamentals of Ozonation...........................................................................…...... 2
Iron & Manganese...........................................................................................….... 2
Disinfection......................................................................................................…... 3
Algae..............................................................................................................…..... 7
Organics........................................................................................................…...... 8
Color.............................................................................................................…...... 10
Tastes & Odor..............................................................................................…....... 10
Turbidity.........................................................................................................….... 11
Reduced Non Metal Species.............................................................................…... 11
Disinfection By-Products of Ozonation

Introduction...................................................................................................…...... 14
Formation of Aldehydes...............................................................................…....... 15
Formation of Carboxylic acids......................................................................…...... 16
Formation of Ketones...................................................................................…....... 17
Formation of Bromoform..............................................................................…...... 17
Formation of Other Ozonation By-products........................................................... 17
Primary Effects of General Disinfection By-products Formation

Introduction.................................................................................................…........ 18
THM’s.........................................................................................................…........ 18
Chloropicrin...............................................................................................…......... 19
Preozonation Effects of Other Treatment Processes

Biological Stabilization..............................................................................….......... 20
Biological Filtration Vs. Adsorption for Ozonation DBP Removal........................ 21
Reaction of Ozone to Lower Chlorine Demand...................................................... 22
Coagulating Effects of Ozone.....................................................................…......... 23
Ozonation Vs. Chlorination

(a summary)...................................................................................…..................... 25
Summary...........................................................................................................….......... 28
©2011 www.aclarus.ca
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List of Acronyms
AOC: Assimilable Organic Carbon

BAC: Biological Activated Carbon
BOD: Biochemical Oxygen Demand
DBP: Disinfectant By-Product
DOC: Dissolved Organic Carbon
GAC: Granular Activated Carbon
NOM: Natural Organic Matter
SOC: Synthetic Organic Compound
TOC: Total Organic Carbon
THM: Trihalomethane
TTHM: Total Trihalomethanes
THMFP: Trihalomethane Formation Potential
HAA: Haloacetic Acid
THAA: Total Haloacetic Acids
TOX: Total Organic Halides
TOXFP: Total Organic Halide Formation Potential
USEPA: United States Environmental Protection Agency
WHO: World Health Organization
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Techniques For Proper Removal Following Ozonation
Problem / Parameter Reaction Product Removal Process

Bacteria / Viruses / Protozoa Dead microorganisms Straight ozonation effective
Sulfide (rotten egg smell)  Sulfate Straight ozonation effective

- soluble - soluble
Iron (taste, staining)  Iron Oxide Post-filtration required to

- soluble - insoluble remove insoluble Iron
precipitate
Manganese (taste, staining) Manganese Oxide Post-filtration required to

- soluble - insoluble remove insoluble Iron
precipitate
Algae (taste, odor, turbidity Kills Algae
eutrophication, aesthetics) 
Organics (turbidity, taste, Coagulating Compounds Post-filtration, settling,
odor)  flocculation effective
Smaller more biodegradable Post-filtration through GAC

compounds (DBP’s) (granular activated carbon)
most effective for DBP s
DBP’s --Disinfection By-products
1
Ozone Reactions With Common Water Quality Parameters

Oxidants (e.g. ozone and chlorine) are added to water and wastewater for disinfection, slime
removal, oxidation of undesirable inorganic species (e.g. ferrous iron, reduced manganese, sulfide,
and ammonia) and oxidation of organic constituents (e.g. taste and odor producing compounds and
trihalomethane precursors. (Standard Methods for the Examination of Water and Wastewater 19 th
Edition).
The fate of oxidants in water and wastewater is complex. Oxidant demand and oxidant
requirement are significantly affected by the chemical and physical characteristics of the sample.
In particular, oxidant (ozone) reactivity is influenced by temperature, pH, contact time, and oxidant
dose. This report only provides a simplified summary of the fate and effectiveness of ozone on
certain water parameters, it must be recognized that water is dynamic and the interrelationships
existing between ozone and water properties are complex.
Introduction
In surface water treatment, the most significant steps are normally particulate removal and
disinfection. Problems with taste and odor, of either natural or industrial origin and the presence
of specific contaminants can also be a concern.
Ozonation is used in drinking water treatment to achieve a variety of treatment goals. The purposes
of ozonation include the following:
1. Disinfection and algae control
2. Oxidation of inorganic pollutants
a. Iron & Manganese
3. Oxidation of organic micro pollutants
a. Taste & Odor compounds
b. Phenolic pollutants
c. Pesticides
4. Oxidation of organic macro pollutants (that is, nonspecific organic targets)
a. Bleaching of color
b. Increasing the biodegrability of organics
c. Destruction of trihalomethane formation potential (THMFP), total organic
halide formation potential (TOXFP), and chlorine demand.
5. Improved Coagulation
Ozone is used in three ways: as a biocide (1), as a classical oxidant (2, 3, and 4a), and as a
pretreatment for improving the performance of subsequent processes (4b, 4c, and 5). (Ozone in
Water Treatment 1991).
For groundwater, the most common treatment process applied, besides disinfection and possibly
softening, is oxidation, for the removal of hydrogen sulphide, ferrous iron, and manganese. The
later two cases require a filtration to remove the precipitate which is formed. (Water Treatment
Principles and Applications).
2
Fundamentals of Ozonation
In an aqueous solution, ozone may act on various compounds in one of two ways:
 by direct reaction with the molecular ozone, and
 by indirect reaction with the radical species that are formed when ozone decomposes in water.
These two properties of ozone enable it to react in three ways:

1) Cyclo addition (Criegee mechanism)
2) Electorphilic reaction
3) Nucleophilic reaction
Cyclo addition:
Ozone molecules may lead to the formation of primary ozonide. The primary ozonide decomposes
into a carbonyl compound (aldehyde or ketone) and a zwitterion that quickly leads to a
hydroxy-hydroperoxide. The hydroxy-hydroperoxide, in turn, decomposes into a carbonyl
compound and hydrogen peroxide. (Ozone in Water Treatment 1991).
Electrophilic reaction:
The electrophilic reaction is restricted to molecular sites with a strong electron density, in
particular certain aromatic compounds. Aromatics substituted with electron donor groups (OH,
NH2 and similar compounds) are highly reactive with ozone (at the ortho and para positions).
Aromatics substituted with electron withdrawing groups (-COOH, -NO2) are weakly reactive with
ozone. (Ozone in Water Treatment 1991).
The initial attack on the substituted positions leads to the formation of ortho- and
para-hydroxylated by-products, although these compounds are highly susceptible to further
ozonation. The compounds lead to the formation of quinoid and, due to the opening of the aromatic
cycle, to the formation of aliphatic products with carbonyl and carboxyl functions.
Nucleophilic reaction:
The nucleophilic reaction is found locally on molecular sites showing an electronic deficit and,
more frequently, on carbons carrying electron withdrawing groups. The molecular ozone reactions
are extremely selective and limited to unsaturated aromatic and aliphatic compounds as well as the
specific functional groups. (Ozone in Water Treatment 1991).
Iron & Manganese:
Iron:
Iron, which is found in both the ferrous (Fe2+) and ferric (Fe3+) state, is the fourth most abundant
element in the earth’s crust. Under reducing conditions in water, the mobile ferrous ion is present
but upon exposure to air, it is oxidized to the less mobile form and precipitated as the ferric ion.
Concentrations of iron in aerated surface waters are usually less than 0.5 mg/L but can be
substantially greater in groundwater.
Few adverse effects are attributable to the presence of iron. In water, iron can discolor cloths,
plumbing fixtures, and cause scaling which encrusts pipes. Excessive concentrations may also
promote bacterial activity in pipes. Iron is however highly objectionable for drinking water
because of its bittersweet astringent taste.
Manganese:
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Manganese is similar to iron in its chemical behavior and is frequently found in association with
iron. Manganese is not usually present in appreciable concentrations in surface water. It seldom
reaches concentrations of 1.0 mg/L in natural surface waters and is usually present in quantities of
0.2 mg/L or less. Higher levels may be found in ground waters, deep lakes, and reservoirs.
Problems attributed by manganese are not considered to be health related, but rather aesthetic and
economic in nature. Concentrations in excess of 0.2 mg/L may make water distasteful to drink.
An objective of less than 0.01 mg/L has been recommended to minimize dark brown or black stains
on fabrics and porcelain.
Iron & Manganese Oxidation:
Iron is oxidized from water extremely fast, however, little manganese oxidation occurs at low
ozone dosages. Manganese oxidation (Mn2+  MnO2) requires more oxidation power than the
conversion of Fe2+  Fe(OH)3, therefore, only after the reduced iron is oxidized does the oxidation
of Manganese begin.
In waters of low organic content, the doses of ozone required to completely oxidize iron and
manganese are close to the theoretical values, 0.43 mg O3 / mg Fe and 0.88 mg O3/ mg Mn,
providing the water contains no other ozone-demanding substances. (Nitrites, or Sulfide).
The presence of organic material in colored surface waters inhibits the removal of Iron and
Manganese, therefore as the TOC organic matter increases, the efficiency of iron and
manganese oxidation decreases. This reduction in efficiency is however buffered by alkalinity, as
seen in the table below.
Alkalinity of the Water (mg CaCO3/L) Required Ozone dose (mg O3/ mg Carbon) to
oxidize 75% of Manganese
50 0.7
200 0.2
(Ozone in Water Treatment 1991).
Disinfection:
Bacteria, viruses, protozoa, worms and fungi are present in the aquatic environment. Water-borne
and water-associated communicable diseases caused by pathogenic organisms include bacillary
and amoebic dysentry, cholera, typhoid and paratyphoid fever, bacterial gastroenteritis,
leptospirosis, infectious hepatitis, poliomyelitis, and diarrhea and enteritis caused by enteroviruses
and protozoans. (Water Quality Source Book 1979).
Because of problems in detecting disease-causing bacteria and viruses, the microbial safety of
water is determined indirectly. Indicator organisms are used to determine the extent of bacterial
contamination, if it can be shown (using indicator organisms) that fecal contamination of the water
has occurred, then pathogenic organisms may also be present. The most commonly used bacterial
indicators are coliforms and fecal streptococci (fecal coliforms).
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High counts of coliform bacteria, especially fecal coliform, indicate the presence of animal wastes,
which may also support pathogenic organisms. Such waters are unsuitable for domestic,
recreational, agricultural, and some industrial applications.
The CT product has been established to define the disinfection efficiency of various chemical
disinfectants. The CT product is based on several individual experiments which are carried out
using different disinfectant concentrations under otherwise identical experimental conditions.
Disinfectant residual concentrations C following contact times T required to attain a certain
specified degree of inactivation.
Disinfection & Ozonation:
Ozone, the most powerful of oxidants, is far superior to chlorine, chlorine dioxide, or chloramines
for the inactivation of all types of waterborne pathogens. Regardless of the pathogen type, the
concentration-times-time (CT) values associated with ozone are orders of magnitude lower than
those associated with any other oxidant.
Table 1 was extracted from Water Treatment Principles and Applications . This table provides
a summary of CT value ranges for 99% inactivation of various micro-organisms by disinfectants at
5oC. From the CT values, it is evident that ozone is the most efficient disinfectant for all types of
micro-organisms.
Table 1 CT values for common disinfectants for 99% inactivation at 5oC

Organism Free Pre-formed Chlorine Ozone Peroxone
Chlorine chloramine dioxide
(pH 6-7) (pH 8-9) (pH 6-7) (pH 6-7) (pH 8)
E.coli 0.034-0.05 95-180 0.4-0.75 0.02 -
Polio 1 1.1-2.5 768-3740 0.2-6.7 0.1-0.2 -
Rotavirus 0.01-0.05 3806-6476 0.2-2.1 0.006-0.6 -
Bacteriophage 0.08-0.18 - - - -
G.lambia 47->150 - - 0.5-0.6 -
G.muris 30-630 - 7.2-18.5 1.8-2.0 1.2-4.4
Bacteria: E. Coli and Salmonella are two of the most common types of bacteria we are exposed to,
and both are very sensitive to inactivation by ozone. The oxidation and bacterial inactivation
reactions which occur upon exposure with ozone occur very quickly, making ozonation very
effective against bacteria.
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Bactericidal efficiency of Ozone at Neully-sur-Marne Plant

Parameter Post filtration Postozonation
Heterotrophic Plate Count / 1580 2.7
mL (72 hour)
Heterotrophic Plate Count / 186 5.4
mL (24 hour)
Total Coliforms / 100mL 3580 0.2
Fecal Coliforms / 100mL 198 0.2
Fecal Streptococci / 100mL 32 0
Sulfate-Reducing Anaerobes 0.7 0.2
/20 mL
Viruses: Viruses are generally more resistant to ozone than vegetative bacteria. Experimental
evidence indicates gram-negative bacteria to be on the order of 10-fold more susceptible than
viruses to ozone. For virus inactivation the CT for chlorine is approximately 6 times larger than the
CT for ozone. (Ozone and Ozone-Peroxide Disinfection of Giardia and Viruses 1992).
Parasites: Giardia and Cryptosporidium are protozoa; their life cycles consist of two forms: fragile
trophozoites and cysts. Trophozoites are too fragile to live in the environment. They stay in the
infected host intestine, where they multiply and encyst. Cysts, the only form found in the
environment, are discharged with feces and disseminate the species. Thus they always enter
waterways through the fecal route, their subsequent ingestion may lead to infection.
Today G. lamblia is widely recognized as the most frequently identified cause of waterborne
disease in North America. The disinfectant concentration (CT) for G. lamblia and G. muris are
0.53 and 1.94 mg.min/L at 5oC, and 0.17 and 0.27 mg.min/L at 25oC for 99 percent inactivation at
pH 7. (Ozone Disinfection of Giardia and Cryptosporidium). These CT values for inactivation of
G. lambia with free chlorine, the chemical disinfectant of choice for many years, are approximately
100 times larger than those reported for ozone. (Ozone and Ozone-Peroxide Disinfection of
Giardia and Viruses 1992).
The USEPA (United States Environmental Protection Agency) stated in a report in 1989 that the
CT requirements for ozone inactivation of 99.9% of G. lambia also achieved a 99.99% inactivation
of viruses. The assumption being made was that if conditions for ozone inactivation of G. lambia
cysts were adequate, viruses would then also be inactivated to the required level. (Ozone and
Ozone-Peroxide Disinfection of Giardia and Viruses 1992).
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Cryptosporidium causes cryptosporidiosis if ingested, an intestinal disease which makes healthy

people very sick, and can kill people whose immune systems have been compromised, as happened
in Milwaukee Wisconsin during the early 1990's. Cryptosporidium is very difficult to remove by
filtration because of its small size. It is also resistant to chemical disinfection, both chlorine and
chloramine have virtually no effect. It is possible that 0.5 log inactivation can be achieved but only
after days of contact with chlorine. Only chlorine dioxide and ozone have been proven to be
effective for the chemical inactivation of Cryptosporidium parvum, and as might be expected
ozone is an order of magnitude more effective than chlorine dioxide. Around 3-6 times more ozone
is required for the inactivation of Cryptosporidium than for Giardia lamblia cysts. (1998 IOA PAG
Annual Conference). Ozone is therefore the only disinfectant capable of inactivating this
microorganism without forming additional halogenated organic by-products of regulatory concern.
CT values for disinfectants to inactivate 99.9% (3 logs) of Giardia lamblia cysts

Disinfectant pH <1oC 5oC 10oC 15oC 20oC 25oC
Free Chlorine 6 165 116 87 58 44 29
at 2 mg/L*
7 326 165 124 93 62 41
8 346 243 182 122 91 61
9 500 353 265 177 132 88
Ozone 6-9 2.9 1.9 1.43 0.95 0.72 0.48
Chlorine 6-9 63 26 23 19 15 11
dioxide
Chloramine** 6-9 3,800 2,200 1,850 1,500 1,100 750
a These CT values will guarantee greater than 99.99% inactivation of enteric viruses.
* CT values will vary depending on concentration of chlorine.
** To obtain 99.99% inactivation of enteric viruses with preformed chloramines requires CT values > 5,000.
CT Levels of Ozone for 99% Inactivation of Cryptosporidium and Giardia

Species Ozone Residual Contact time (min) CT for 99%
(mg/L) inactivation
(mg.min/L)
C. parvum 0.77 6 4.6
(Cryptosporidium)
C. parvum 0.51 8 4
C. parvum 1.0 5 and 10 5-10
C.baileyi 0.6 and 0.8 4 2.4-3.2
C. parvum 0.44 6 2.6
C. parvum 3 6 18
C. parvum 5 2 10
G. lamblia (Giardia) 0.11-0.48 0.94-5 0.53
G. lamblia 0.03-0.15 1.06-5.5 0.17
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Peeters (1989) found an ozone concentration of 1.1 mg/L for 6 minutes sufficient to disinfect water
containing 100,000 oocysts / mL, while some cysts remained viable after 30 minutes contact time
with 0.43 mg/L of chlorine dioxide. Korich (1990) used mouse infectivity to show that 90 percent
inactivation could be achieved after 5 min contact with 1 mg/L ozone. This gave a CT value of 5
mg.min/L as compared to 78 mg.min/L for chlorine dioxide and 7200 mg.min/L for chlorine and
monochlorine. (Ozone in Water Treatment 1991).
Ozone is also very effective against free-living amoebae trophozoites (Naegleria and
Acanthamoeba), values for 99 percent inactivation at 20oC are less than 0.1 mg . min/L. Free living
Amoebae are parasites that occur in the environment both as cysts and as the more fragile
trophzoite form.
CT values for 99 percent inactivation of free living amoeba cysts with Ozone, Free Chlorine,
and Chlorine Dioxide
Oxidant Micro-organism CT (mg . Min/L) Difference (%) from
Ozone
Ozone N. gruberi 0.70 ---
Free Chlorine N. gruberi 27 3857%
Chlorine Dioxide N. gruberi 5.51 786%
Algae:
Algae, or more accurately plankton create several problems including:
 algal blooms
 poor coagulation and flocculation
 poor settling characteristics
 various odors and tastes
 some species may by toxic
 whether living or dead can be responsible for bacterial growth
Ozone is effective at killing microorganisms, including algae, because of its strong oxidizing
capabilities targeting the cell membrane. Ozone is also capable of inactivating certain
zooplankton, including certain mobile organisms like Notholca caudata. In order to remove such
organisms by either flocculation or filtration, they must first be inactivated. The table below
illustrates the advantage of inactivation as a preliminary step in the removal of certain types of
plankton.
Inactivation of Notholca caudata by Oxidation
Oxidant Dose (mg.L) Reaction Time (min) Inactivation %
Ozone 1 1 14
2 1 64
3 1 70
1 5 26
2 5 72
3 5 76
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Organics:
Organic compounds belong to one of two groups; large molecules produced by natural processes
(humic acids, fulvic acids, and proteins), or small molecules (monomers of larger particles, and
synthetic organic chemicals). Complete oxidation converts a specific organic compound to carbon
dioxide and water. These oxidation processes that take place are rarely complete. The more
reactive organic compounds (phenols, dyes, aromatics containing OH and NH2 groups, alkenes,
alkynes, and amines) are often partially oxidized to form more stable compounds, such as
aldehydes, ketones, organic acids, and alcohols.
Reactions with aquatic humic substances:
Natural waters contain varying concentrations of numerous organic and inorganic compounds.
The main organic constituents in natural water are a collection of polymerized organic acids called
humic substances, as well as, carboxylic acids, amino acids, and carbohydrates. The
concentrations of these compounds is very important in determining the ozone demand of a water
because of their reactiveness with ozone. More importantly it is these substances which can create
taste and odors in water or possibly cause adverse health effects.
Aquatic humic substances (humic and fulvic acids) have been used to represent natural organic
matter. These compounds are the result of the degradation and polymerization of vegetation.
Aquatic humic substances are complex, their main physiochemical properties include:
 a strong reactivity with halogens, leading to a high consumption of chlorine and
 production of several volatile and nonvolatile halogenated organic compounds.
 a significant adsorbability on solids such as activated carbon and alumina.
 possible complexation with trace metals, hindering their removal.
 possibility that the humic substances may combine with organic micro pollutants, including
some pesticides.
Based on what is known at this time, the action of ozone on aquatic humic substances in a neutral
pH solution leads primarily to:
 a slight abatement in TOC
 a strong degradation of color
 a slight decrease in the high molecular weight fractions, and a slight increase in the smaller
fractions
 a significant increase in the carboxylic functions
 the formation of ozonation by-products
Non volatile ozonation products derived from humic substances include:

humic acid---aromatic compounds (acids, carbonyl derivatives)
fulvic acid---aliphatic compounds (alcohols, acids, diacids, linear alkanes, substituted
aromatics)
These reactions as a whole lead to a slight loss of organic carbon and a decrease in the average
apparent molecular weight of the humic matter. Simultaneously, ozonation induces a distinct
increase in acidity through the carboxylic functions; a formation of trace amounts of some aliphatic
acids, aldehydes, alkanes, and other products; and finally the removal of color.
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Reactions with Synthetic Organic Chemicals:
Micro pollutants present in water may include: aromatics and aliphatic hydrocarbons, chlorinated
solvents, phenols, substituted or nonsubstituted polyphenols, pesticides, plasticizers, and
surfactants. Micro pollutants generally only make up around 5% of the total organic carbon (TOC)
in surface waters. (Ozone in Water Treatment 1991).
Ozone reacts first with multiple bonds (C=C) or atoms carrying a negative charge (N, P, O, S, and
nucleophilic carbons). A strong initial reactivity is therefore predicted for ortho-activated
aromatics by substituents such as OH, CH3, or OCH3. A weaker initial reactivity is predicted for
molecules with NO2, CO2H, or CHO groups. (Ozone in Water Treatment 1991).
Ozonation can remove many SOC’s (biocides, hydrocarbons, phenols, plasticizers, dyes, amines,
aromatics, pesticides, and solvents). This removal leads to the chemical transformation of these
molecules into toxic or non-toxic by-products. It should be noted that these compounds occur at
very low concentrations.
Micro pollutants and their reactivities with ozone

Organic Compounds Type Reactivity with Ozone
Hydrocarbons (Aliphatic & Alkanes Unreactive
Halogenated)
-reactivity increases with
multiple bonds
-substitution makes substance
less reactive
Alkenes Slightly reactive
Alkynes Reactive
Alcohols, Ethers, Aldehydes, Esters and Carbonyl groups Unreactive

Carboxylic acids
Aromatic Compounds Possessing OH or NH2 group Reactive

(phenol & aniline)
Possessing NO2 or Cl group Much less reactive
Phenols and derivatives Strongly reactive (Initial

by-products are of greater
toxicity)
Amines and derivatives Strongly reactive (produces

chloropicrin)
Pesticides Chlorinated organic Slowly reactive
Organophosphorus Reactive
Herbicides Phenoxyacetic Strongly reactive
Surfactants (chief active Not readily oxidized

product in detergents)
Dyes (related to the presence of Strongly reactive

fluvic materials)
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Color:
Water appears to be colored when dissolved matter absorbs light or when suspended particles
scatter light. The color of water is attributable to the presence of organic material (e.g. algae,
protozoa, decaying vegetation) and inorganic material (e.g. iron and manganese). Color is not
normally considered a serious problem, although a limit of 15 TCU has been set for aesthetic
reasons.
Ozone doses of 1-3 mg O3/ mg C lead to almost complete color removal. Many studies show that
for water with a color between 20 and 50 Pt-Co units, the application of only 1 mg O3/L will lead
to a color abatement of about 10 Pt-Co units. Klimkina (1987) used ozone doses of 8-13 mg O3/L
and experienced a color removal of between 20 - 60%. (Ozone in Water Treatment 1991).
Oxidation with chlorine and chlorine dioxide can lead to satisfactory color abatement, but ozone
remains the most efficient oxidizer . (Ozone in Water Treatment 1991).
Tastes and Odor:
Odor and taste of water are closely associated and it is difficult to clearly differentiate between
them. Neither parameter assesses the safety of drinking water but both determine its consumer
acceptability.
Used by itself, ozone can sometimes solve taste and odor problems. However there are some
compounds which are responsible for giving water a taste, or an odor which cannot be oxidized
(saturated compounds).
Inorganic compounds such as iron, copper, and zinc can be tasted in distilled water at
concentrations of 0.05, 2.5, and 5 mg/L respectively (Cohen 1960). However only iron is likely to
be present at such concentrations in potable water. Hydrogen sulfide may also cause characteristic
tastes, often described as smelling like rotten eggs. Both reduced sulfur compounds and iron may
be eliminated by oxidation with ozone.
In the majority of cases odors are attributable to organic compounds present in very small
concentrations. Many compounds fall into this category, many stemming from the decomposition
of organic matter, most however are produced by specific organisms. The organisms responsible
for creating taste and odor in water are principally actinomycetes and blue-green algae
(cyanobacteria). For example, synura (a species of algae) produces unsaturated aldehydes, which
are important odor by products, and are readily oxidizable by ozone.
However, ozone can form aldehydes from organic compounds already in the water supply which
may have fruity or fragrant odors.
The effect of ozonation and subsequent treatment on the taste threshold number at
11
the Saint-Maur Pilot Plant (France) can be seen in the table below.
Treatment Average Taste Threshold Flavor Reduction (%)

Raw water 10 --
Settled water 7 30
Filtered water 5.3 47
Filtered water with ozone 3.3 67
Sand without ozone 3 70
Sand with ozone 3 70
Sand & activated carbon without ozone 2.8 72
Sand & activated carbon with ozone 1.8 82
Activated carbon without ozone 2.3 77
Activated carbon with ozone 2.8 72
Turbidity: (Particulate removal)
Turbidity is a measure of the suspended particles such as silt, clay, organic matter, plankton, and
microscopic organisms in water which are held in suspension. See section on the coagulating
effects of ozonation on page 28.
Reduced Non-metal species:

It is thermodynamically possible for ozone to oxidize chloride, bromide, and iodide.
Oxidation-Reduction potentials
Species Oxidation-Reduction Potential (Eo) V
O3/O2 2.07
HClO/Cl- 1.49
HBrO/Br- 1.33
HIO/I- 0.99
The reactions which take place with bromine species (Br-, BrO-, BrOO-) occur in a two steps
forward one step back fashion. Although bromide is oxidized to produce BrO-, and BrOO-
bromide (Br-) is also produced, creating a cyclical effect. However practically no Bromide
oxidation will occur until all other ozone demanding substances are first eliminated, especially
organic materials. See section on formation of bromate of page 22.
At a given pH the rate of free chloride oxidation by ozone is greater than the rate of free bromine
oxidation. This is because the cyclic nature of bromine oxidation does not occur with
chloride. This is evident when one examines the half lives of each substance.
12
Species Concentration of Ozone Half life (minutes)

Chlorine 1 mg / L O3 15 minutes
Bromine 1 mg / L O3 60 minutes
Ammonia is also oxidized by ozone albeit very slowly, producing nitrate (which can cause
methaemoglobomaemia). The oxidation of ammonia is also catalyzed by the presence of bromide.
Through a series of reactions involving ammonia species and bromide species additional bromide
and nitrate are produced.
Nitrite is also oxidized by ozone at a rate constant of 3.3-3.7 X 10^5 M^-1s^-1. The reaction
corresponds to a consumption of 1.04 mg ozone / mg nitrite. The product of this reaction is once
again nitrate.
Sulfide competes with other substances for ozone, its tenacity to acquire ozone can substantially
increase the ozone requirement a sample. The oxidation into sulfate (S2-  SO32-  SO42-)
corresponds to a consumption of 6 mg ozone / mg S^2-. As with other compounds, the reaction
rates decrease with the degree of anion protonization. As species combine with other elements to
form more stable combinations (compounds) it becomes more difficult to break their bonds,
reducing the rate of sulfate oxidation.
Maximum Acceptable Levels in Water Used for Domestic Consumption

Bacteria, Fecal Coliform 0 CFU/100mL
Bacteria, Total Coliform 10 CFU/100mL
Color 15 TCU
Iodine 10 Bq/L
Iron 0.3 mg/L
Manganese 0.05 mg/L
Nitrate + Nitrite 10.0 mg/L
Nitrite 1.0 mg/L
Turbidity 5 NTU
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General Ozone Reduction Efficiency

Parameter Ozonation Reduction Efficiency
Iron Very Effective (Effectiveness reduced with high levels of organic

matter)
Manganese Effective after the removal of Iron has occurred (Effectiveness

reduced with high levels of organic matter)
Turbidity Very effective (when post-ozonation-filtration is used)
Coagulation Greatly improves coagulation / filtration efficiencies
Color Effective
Algae Effective, but species dependant
General Disinfection Very Effective
Bacteria (E.Coli, Salmonella, & Very Effective

Legionella pneumophila)
Giardia Effective, when a residual ozone concentration is produced
Cryptosporidium Effective (contact time more relevant than residual ozone

concentration)
Amoeba Cysts (Naigleria Very effective

Acanthamoeba)
Total Organic Carbon Very poor (only small organic fraction bonded around clay
particles)
Dissolved Organic Carbon Poor (will remove some through increased flocculation and
subsequent filtration)
TOX (total organic halides) Effective
THM (Trihalomethane Effective against the formation potential of THM’s

–disinfectant by-products)
Taste and Odors Effective, but site (problem) specific (Effective for Iron, Hydrogen
sulfide, most micro-organisms)
BOD Very Effective
Bromide Effective only after complete organic removal (bromoform

produced)
Chloride Oxidation 4 times faster than Bromide (Oxidation changes Cl

species composition)
Cyanide Very Effective
Ammonia Oxidation Slow (reaction product nitrate)
Nitrite Oxidation Fast (reaction product nitrate)
Sulfide Large Ozone demand (high ozone doses required)
Iodide Oxidation fast
14
Disinfection By-Products of Ozonation

Introduction
It has been known for some time that the process of chlorine disinfection produces large numbers
of (mostly chlorinated) by-products, and that some of these by-products, although present at very
low levels, are mutagenic and carcinogenic (Ozone in Water Treatment 1991, Trihalomethanes in
Drinking Water - World Health Organization 2005). The fact that chlorination produces
chloroform and other THM’s has led to a search for alternative methods of drinking water
disinfection, with ozonation being one of the most frequently mentioned choices. (Ozone in Water
Treatment 1991).
The utilization of ozone as a public drinking water disinfectant is not likely to expose the public to
ozone itself but rather to ozone reaction by-products. Ozone reacts with natural products in the
water supply (e.g. humic acids) to form numerous disinfection by-products. The common opinion
holds that the reaction by-products of ozonation appear to be less toxic than those produced by
chlorination. For example, ozonation does not produce THM’s in water and in fact can destroy
THM precursors. Likewise, ozonation of humic acids does not produce chlorohydroxyfuranones,
highly mutagenic reaction by-products of chlorination. (Ozone in Water Treatment 1991).
The reaction of ozone with organic material is extremely complex and can vary greatly, depending
on the substrate and other conditions. As mentioned, ozone is an extremely powerful oxidant that
can break down long-chain organic molecules. Several studies identified a number of aliphatic
aldehydes, mono- and dicarboxylic acids, mono- and diketones, alkanes, organic peroxides,
epoxides, unsaturated aldehydes, and phthalates as potential by-products of ozonation. (Ozone in
Water Treatment 1991). The range of disinfection by-products is likely to depend on the chemical
characteristics of the untreated water, which in turn will affect the toxicological properties of the
finished water.
Ozonation by-products being considered for regulation include aldehydes (formaldehyde,

acetaldehyde, hexanal and heptanal), organic acids, ketones, epoxides, peroxides, nitro-samines,
N-oxy compounds, quinones (polyhydroxy phenols) and bromine-substituted compounds. (Water
Treatment Principles and Applications).
Oxidation process of organic matter:
At most ozonation doses the oxidation of humic and fulvic materials is rarely complete. Meaning
that the compounds will have been broken down to a degree, but not to the extent of a full oxidation
reaction, which produces water and carbon dioxide only. Common by-products of ozonated humic
material are characterized by a mixture of lower-molecular-weight, more polar products and
high-molecular-weight products remaining closer in identity to the original material. Among the
intermediate products formed, when ozone attacks the organic matter present in raw waters, are
low-molecular-weight by-products such as aldehydes. If oxidized further, these aldehydes can
produce aldo-acids and carboxylic acids. Formaldehyde, a ubiquitous component of the
environment, may be introduced into drinking water by ozone treatment. (Standard Methods for
the Examination of Water and Waste Water 19th Edition).
Alcohol (oxidation)  Aldehyde / Ketone (oxidation)  Carboxylic acid
15
Formation of Aldehydes:
Aldehydes are characterized by the presence of the carbonyl group at the end of the hydrocarbon
chain. The removal of two hydrogen atoms from an alcohol, during oxidation, yields an aldehyde.
Aldehydes can be oxidized into fatty acids which contain the same number of carbons as in the
initial aldehyde. The oxidation of a primary alcohol gives the corresponding aldehyde.
e.g. methyl alcohol  (oxidation) formaldehyde (propanal)  (oxidation) formic acid

e.g. ethyl alcohol  (oxidation) acetaldehyde
All aldehydes exhibit the following properties: (exception gaseous formaldehyde)

1) all aldehydes up to C11 are neutral, mobile, volatile liquids.
2) all aldehydes above C11 are solids under ambient conditions.
3) formaldehyde and liquid aldehydes have a unpleasant, pungent, irritating odor.
4) solubility decreases with increasing molecular weight.
There are two postulated mechanisms for aldehyde formation during ozone treatment. The first is
a two-step (Criegee) attack at unsaturated C-C bonds by molecular ozone, with ozonide or
epoxides formed as intermediates. The second involves an indirect (less selective) reaction of
radicals. Although the levels of aldehyde formation are usually a function of ozone dose, their
concentrations are often controlled in water treatment by increasing the pH and thus the alkalinity
of the water. (Standard Methods for the Examination of Water and Waste Water 19th Edition).
Aldehydes are unlikely to pose a serious health hazard to the consumer at ug/L concentrations as
usually encountered in drinking water treatment. However, they react with nucleophiles even at
these low levels and can therefore be a potential threat. Thus, for example, formaldehyde,
acetaldhyde, and crotonaldehyde are known animal carcinogens. Formaldehyde is a known human
carcinogen. (Standard Methods for the Examination of Water and Waste Water 19th Edition).
In addition to their possible effects on human health, higher-molecular-weight aldehydes have

been linked to fruity, fragrant, and orange-like odors in treated waters. In general C1 to C14
aldehydes have been reported to increase upon ozonation. Although other studies (Van Hoof 1985
and Glaze 1989) have indicated lower-molecular-weight aldehydes may also increase in
concentration, including formaldehyde and acetaldehyde.
Aldehyde Formation in a Full-Scale Ozonated Surface Water

Aldehydes Raw water concentration (ug/L) Ozonated water conc. (ug/L)
Formaldehyde 3.2 28.3
Acetaldehyde Non detected 9.7
Propanal Non detected 2.7
Butanal Non detected 4.1
Pentanal Non detected 15.2
Heptanal 4.6 3.7
Glyoxal Non detected 13.0
Methyl Glyoxal Non detected 28.3

16
Aldehyde Formation at the Los Angeles Aqueduct Filtration Plant (concentrations in ug/L)
Aldehydes 1 mg/L Ozone 1 mg/L Ozone 1 mg/L Ozone 1 mg/L Ozone
Raw water Post ozonation Raw water Post ozonation
Hexanal Non detected 130 8 578
Heptanal Non detected 195 Non detected 2,900
Octanal Non detected 48 47 214
Nonanal 55 107 139 618
Decanal 199 270 615 1,130
Undecanal Non detected Non detected 75 495
Dodecanal Non detected Non detected 14 155
Tridecanal Non detected Non detected 4 233
Tetradecanal Non detected Non detected 16 258
Schalekamp (1978) investigated ozone dose dependency and found that aldehyde formation
peaked near 5 mg/L ozone dose, after which aldehyde concentration fell off. (Ozone in Water
Treatment 1991).
Formation of Carboxylic acids:
Carboxylic acids are characterized by the presence of the carboxyl group (-COOH), in terms of
structure a carboxylic acid may be aliphatic (straight chain derivative of methane), carbocyclic (or
aromatic), and heterocyclic.
Carboxylic acids may be classified in terms of the number of carboxyl groups (mono, di, tri, and
tetracarboxylic acids. When a carboxylic acid contains a hydroxyl group in addition to that of the
principal -COOH group, the term hydoxy is used.
A carboxylic acid may also be classified in accordance with the number of available hydrogens for
salt formation. If only one hydrogen is available, the acid is monobasic...
There are several series of carboxylic acids including: saturated monobasic fatty acids, unsaturated
monobasic fatty acids, propioloic acid series, dicarboxylic acids, hydroxymonocarboxylic acids.
Carboxylic acids can be formed through oxidation in three ways:

1) oxidation of relevant alcohol e.g. ethyl alcohol  acetic acid
2) oxidation of relevant aldehyde e.g. formaldehyde  acetic acid
3) oxidation of relevant alkyaromatic e.g. toluene  benzoic acid
17
Concentration of low-molecular-weight monocarboxylic acids (<C13) and dicarboxylic acids have

been shown to increase upon ozonation. As with aldehydes, the formation of acids is highly
dependent on the nature of the organic matter present in the water or the concentration of free
radical scavengers. Lower ozone doses lead to the formation of Aldehydes; higher ozone doses
lead to the subsequent formation of acids as the aldehydes break down. However acids can also be
formed from high-molecular-weight acids, as well as, humic materials and other natural organic
matter.
Formation of Ketones:
Ketones are characterized by the presence of the carbonyl group bonded to two carbon atoms in the
hydrocarbon chain. Ketones are isomers of aldehydes with the same number of carbon atoms.
(same number of each atom, only in a differing position giving it distinct properties).
The oxidation of a secondary alcohol yields a secondary ketone (alphyl ketone).
e.g. CH3--CH3 (OH)--CH3  CH3--CH3 (O)--CH3
e.g. propyl alcohol (propione) (oxidation)  acetone (oxidation)  acetic acid
Ketones may also be produced from aromatic alcohols as in the case of benzophenone C6H5--C
(O)--C6H5 (aromatic or diaryl ketone). There can also be mixed ketones as in the case of
acetophenone (phenylmethyl ketone) C6H5--C(O)--CH3 (aryl-alphyl).
Upon oxidation Ketones decompose to form two acids, each acid will contain fewer carbon atoms
than the originating Ketone.
Formation of Bromate:
Bromate formation is expected to be the most important by-product issue regarding ozonation.
Concern over the health effects of bromate ion has led to increased scrutiny of bromate ion
formation during water treatment. It has been shown that the bromate ion (BrO3-) is a animal
carcinogen, it then must become a suspected human carcinogen as well.
Although it is well known that ozone itself will not produce chlorinated organic by-products, small
amounts of bromoform or more importantly bromate may be produced in the presence of bromide.
This is a result of ozone’s ability to oxidize bromide to bromine. This probably does not occur
where organic matter can effectively compete for ozone. However, when high ozone doses are
used, and the highly reactive organics become exhausted, oxidation of bromide may occur, leading
to the formation of bromate and bromoform. (Ozone in Water Treatment 1991). Therefore, over
ozonation will lead to the formation of harmful bromate, if the water originally contained high
levels of the bromide ion.
Reduced bromate formation can be accomplished primarily in two ways: (1) reducing the pH or,
(2) reducing the ozone dose and increasing the contact time (to conserve CT values).
Formation of other ozonation by-products.

With the Creigee mechanism organic peroxides (e.g. hydrogen peroxide) are anticipated
intermediates, however quite unstable. Other by-products of ozonation are phthalates, alkanes, and
phenols.
A major factor contributing to biological instability (bacterial regrowth within the distribution
system) is the concentration of easily biodegradable or assimilable organic carbon (AOC) in the
water. The concentration of the material is usually increased upon ozonation. (Water Treatment
Principles and Applications). This means that if the water after ozonation has to be run through a
distribution system of significant length regrowth of some micro-organisms may occur.
18
Primary Effects on General Disinfection By-product Formation
Introduction
This section deals with the effects of ozone on the by-products of chlorination. The most common
chemical disinfectant in use today is chlorine. It has been known for some time that the process
of chlorine disinfection produces large numbers of (mostly chlorinated) by-products, and the that
some of these by-products, although present at very low levels, are mutagenic and carcinogenic.
(Ozone in Water Treatment 1991). The fact that chlorination produces chloroform and other
THM’s has led to a search for alternative methods of drinking water disinfection, with ozonation
being one of the most frequently mentioned choices. (Ozone in Water Treatment 1991).
Ozone does not readily react with trihalomethanes (chloroform, dichlorbromethan,

chlorodibromomethane, and bromoform), however some losses will result due to volitization.
Other chlorination by-products besides the THM’s may be more susceptible to ozone attack. For
example, low doses of ozone can directly reduce instantaneous TOX (total organic halides)
concentrations in partially treated water by as much as 50%. (Bruchet et al. 1985). (Ozone in
Water Treatment 1991). TOX is a measurement used to estimate the total quantity of dissolved
halogenated organic material.
THM’s:
Typically Trihalomethanes (THM’s) are produced in the treatment process as a result of

chlorinination. Only four THM compounds are normally found: chloroform (CHCl3),
bromodichloromethane (CHBrCl2), dibromochloromethane (CHBr2Cl), and bromoform (CHBr3).
Toxicology studies suggest that chloroform is a potential human carcinogen. (Standard Methods
for the Examination of Water and Waste Water 19th Edition).
It is anticipated that the current THM guideline of 100 ug/L will be revised to a lower value. If the
Canadian value were to be set in the range of the World Health Organization (WHO) or that of
Germany, 30 and 25 ug/L respectively, it would virtually eliminate the use of chlorination as the
main disinfectant for many water supplies. Chlorine could still be used for distribution system
protection, provided the chlorine demand was sufficiently reduced by physical and biological
means. (Water Treatment Principles and Applications).
Ozone effectively reduces THM precursors at low pH’s. As the concentration of bi-carbonated
increases (around a pH 10), and the molecular ozone attack pathway is favored, the THM
formation potential increases. Generally, however, the pH of surface waters is much lower than 10
and preozonation will effectively reduce the potential for THM formation. At a neutral pH (7) the
formation potential of THM’s is slightly reduced by 3-20 % (at the most common ozone dosages).
(Ozone in Water Treatment 1991). Therefore, ozone when used prior to chlorination can
significantly reduce the formation of THM’s upon subsequent chlorination.
Note: The THM formation potential is the difference between the final total THM
concentration and the initial total THM concentration.
19
Chloroform:
The precursors concentrations of chloroform are reduced by ozonation. In one study, (Miltner
1990) precursors of chloroform reduced by as much as 39% upon ozonation. (Ozone in Water
Treatment 1991).
Because THM’s are regulated as a group, finished water instantaneous total THM’s are often
reduced as a result of ozonation. In high bromide waters, however, this would likely not be the
case.
Formation of Chloropicrin:
Chloropicrin precursor concentrations are thought to be enhanced by ozonation at neutral pH. The
oxidation of amines and the formation of highly reactive nitrogen pentoxide ( in the ozone
generator of corona discharge generators) are thought to be responsible for the enhancement of
chloropicrin. Thus, the use of pure oxygen may help reduce the formation of chloropicrin
precursors, however ,oxidation of amines is not affected by the use of pure oxygen and will
evidently lead to the formation of chloropicrin.
Possible By-Products of Ozonation

Parameter Characteristics Toxicity
Aldehydes contain the carbonyl group Formaldehyde is a known
human carcinogen
Ketones (mono & di) contain the carbonyl group
Carboxylic acids (mono & contain the carboxyl group
di) -COOH
Alkanes 1) saturated carbon-carbon
bonds e.g. methane
Organic peroxides
Epoxides 1) ozone decomposition
intermediate
Phthalates
Bromoform/Bromate 1) produced upon oxidation of Bromate is a known human
bromide carcinogen
Chloropicrin (precursors)
20
Preozonation Effects on Other Treatment Processes
Biological Stabilization
Biological processes have been found to remove color, taste and odor, disinfection by-products,
and disinfection by-product precursors. In addition, the promotion of biological activity in a
treatment plant can help prevent uncontrolled growth in distribution systems. This is especially
important for plants using oxidative treatments such as ozonation, which may enhance the
biodegradability of natural organic matter. Greater biological stability may partially eliminate the
need for maintaining a disinfection residual in the distribution system and thereby further reduce
the presence of disinfection by-products.
Many of the dissolved organic compounds are not significantly reduced by conventional treatment
(e.g. flocculation, settling, rapid-rate filtration). Biological treatment can remove biodegradable
compounds that would otherwise be a food source for bacteria present in the distribution network.
The growth of bacteria ultimately leads to the development of higher organisms such as Asellae.
Moreover, biological treatment permits lower doses of chlorine to be added in order to maintain
free chlorine residual at the end of the distribution network, thus decreasing the risks of THM and
odor formation.
In North America biological processes have not been extensively used due to a perception that
encouragement of bacterial growth contradicts the principal objective of water treatment, which is
to eliminate human pathogenic organisms. However bacterial populations on granular media can
use a wide variety of organic compounds.
Biodegradable or assimilable organic carbon is defined as either (1) the fraction of dissolved
organic carbon (DOC) that can be used by the bacteria for growth and cell maintenance or (2) the
degree to which microbial growth is stimulated by the DOC.
Numerous authors have shown evidence of the increase in the biodegradability of dissolved natural
organic matter following ozonation.
Effect of Ozonation on Biodegradability in Several Drinking Water Plants

Plant Before Ozone After Ozone % Increase
Kralingen 0.025 0.173 692

(Netherlands)
Weesperkarspel 0.012 0.108 900

(Netherlands)
Choisy-le-Roi (France) 0.41 0.71 173
Neuilly-sur-Marne 0.32 0.56 175

(France)
Choisy-le-Roi (France) 0.46 0.70 152

21
Certain molecules are either resistant to the action of ozone or are transformed into products that
remain nonbiodegradale. However, many natural organic compounds show substantial
improvements in biodegradability at doses of 0.5 mg O3/ mg DOC. Studies of the ozonation of
simple aromatic compounds have shown that little change occurs in biodegradability with partial
oxidation, whereas at higher ozone doses, ring cleavage occurs and biodegradability increases
greatly. The same appears to be true tor much of the organic matter in natural waters. Beyond 2
mg O3/ mg DOC, in most cases, all the biodegradable organic carbon likely to be formed has
already been transformed. This ozonation dosage of 1 mg O3/ mg DOC falls within the range of
doses currently applied in full-scale water treatment plants. (Ozone in Water Treatment 1991).
Biological Filtration Vs. GAC Adsorption for Ozonation DBP Removal
Ozonation prior to GAC:
During ozonation some of the biorefactory organics are converted to more biodegradable materials
through oxidation. Polar oxygen groupings are added to some of the dissolved organics, and some
of the larger dissolved organic molecules are cleaved into smaller oxygenated fragments by the
oxidative action of ozone. When these more readily biodegradable organic molecules pass through
GAC columns, they encounter natural microorganisms, which develop in GAC macropores within
only a few weeks, and thrive in the absence of a residual disinfectant. These microorganisms are
capable of rapidly mineralizing the biodegradable organics, converting them to carbon dioxide and
water in a few minutes of empty bed contact time.
Ozonation prior to granular activated carbon (GAC) adsorption sometimes leads to lower
steady-state TOC concentrations following break-through. Research has shown that the improved
TOC removal is a result of increased biological activity on the GAC that occurs when influent
water is ozonated and the organics are rendered more biodegradable. Several studies (Ozone in
Water Treatment 1991) have demonstrated a significant improvement in DOC, THMFP, and
TOXFP adsorption following preozonation.
Ozonation prior to slow sand filtration:

Slow sand filters generally have a thick layer of microbiota, called the schmutzdecke, on the upper
sand surface. Ozonation prior to slow sand filtration can lead to significant THMFP and TOC
removals even hen sand filtration or ozonation alone does not have an important effect.
A study was conducted in Winnipeg, Manitoba by Paul Wobma of CH2M to evaluate the
effectiveness of biological filtration for DBP (disinfectant by-product) removal and to determine if
GAC is required for DBP removal on a continuous basis.
Although ozone DBP’s are readily adsorbed by GAC, the Winnipeg study showed they are also
easily biodegraded. BAC filtration can effectively remove >90% of the post-ozone aldehydes.
After ozone and BAC the finished water aldehyde levels are essentially the same as the raw water
levels and are normally less than 10 ug/L. Keto acids are biodegradable with the BAC filter
effectively removing 80 to 100% of the post-ozone keto acids. With respect to carboxylic acids,
the Winnipeg study also showed that acetate is easily biodegraded. For formate, it may have taken
the BAC biomass longer to reach steady state for formate than for aldehydes or keto acids. BAC
removal of formate during the month of July of the study was 75%. In all cases, biofiltration with
anthracite media is not as effective as BAC with normal removal of 10-40%. (1998 IOA PAG
Annual Conference).
22
The Winnipeg study also showed that if chlorination continues without GAC absorption the short
term TTHM target of 100 ug/L is achievable, but the long term goal of 40 ug/L cannot be achieved.
Biofiltration was found to be ineffective for THM removal and seasonal GAC adsorption will be
required if removal will be required in the future.
HAA’s ( haloacetic acids) are not removed by ozonation, but are easily adsorbed and biodegraded.
With BAC alone the long term target of 30 ug/L THAA is also achievable in both warm and cool
seasons. (1998 IOA PAG Annual Conference).
Reactions of Ozone to Lower Chlorine Demand
Ozone acts to lower both the precursor material concentrations and the chlorine demand of the
water. Resulting in a decrease in the formation of disinfection by-products which can be health
hazardous (e.g. trihalomethanes, haloacetic acids, and halogenated organics). It can also result in
lower formation of taste and odor compounds, which may not have implications of the by-products
but are certainly undesirable.
Preozonation can be used in place of prechlorination allowing for the (1) delay the application of
chlorine, (2) reduce the chlorine dose, (3) eliminate chlorine entirely in favor of an alternative
secondary disinfectant. Shifting the point of chlorination can lead to reductions in by-product
concentrations.
Ozonation prior to chlorination:
The ability of Ozone to inactivate Cryptosporidium makes its use attractive to water treatment
operators. When used in combination with other less reactive oxidants (chlorine, or chloramines),
increased pathogen kill is observed. A similar effect is observed for ClO2 (chlorine dioxide). By
comparison, Ozone provides faster inactivation and a greater log kill of Cryptosporidium than
chlorine dioxide.
If ozone and chlorine dioxide are to be used in combination, it is important that chlorine dioxide
application follow the ozone treatment to prevent the formation of unwanted by-products such as
ClO3-.
A second consideration is the presence of hydrogen peroxide. If H2O2 is present (under basic
conditions), the peroxide ion (HO2-) will reduce chlorine dioxide to form chlorate ion (ClO2-), all
but eliminating any enhanced disinfection capability expected from using multiple oxidants.
Ozone and chlorine dioxide react in solution even at the mg/L level, this implies that on the several
seconds and greater time scale, ozone and chlorine dioxide cannot exist simultaneously in solution.
23
Coagulating Effects of Ozone
Coagulation:
Particulate removal begins with coagulation, which involves the addition of a chemical to
neutralize the charges on particles and facilitate their agglomeration during the slow mixing
provided in the flocculation step. Coagulation also helps prepare the particles for filtration. (Water
Treatment Principles and Applications).
Many of the particles that must be removed in water treatment are very small and are referred to as
colloids. These particles carry an electric charge an their surface: because of their small size this
surface charge has an important influence on their behavior. Because of the particles carry the
same charge (usually negative), they tend to repel one another. The purpose of coagulation is to
neutralize these charges so that the particles can combine to form large agglomerations if they
contact one another. Larger particles settle much faster, and in addition neutralized particles are
much more susceptible to filtration. Coagulation is always followed by a period of low-energy
mixing called flocculation, which promotes particle-particle contact and the growth of particle
aggregates known as flocs. If sedimentation is used flocculation will occur in a separate chamber,
if filtration is used flocculation may take place in the liquid above the filter, or even in the pores of
the filter. (Water Treatment Principles and Applications).
The most common chemical coagulants include aluminum salts (e.g. alum, and polyaluminum
chloride), iron salts, and organic polymers.
Coagulation & Ozonation:
Particulate removal can be accomplished through the coagulating effects of ozonation. This
phenomenon may take the form of a wide range of secondary effects, such as a shift in particle size
distribution towards larger sizes; the formation of colloidal particles from dissolved organic
matter; the improved removal of TOC or turbidity during subsequent settling, flotation, or
filtration; a decrease in coagulant dose necessary for achieving desired effluent turbidity or TOC;
an increase in floc settling velocities; and extended filter run length due to slower head loss buildup
or delayed breakthrough. (Ozone in Water Treatment 1991). These are called secondary effects
because they do not occur instantly at the moment of ozone reaction, but begin to manifest
themselves. What this all means is that the clarity of the water will improve and material will settle
out of suspension. This benefit of ozonation may be achieved at a relatively low ozone dose of 0.5
- 1.5 mg/L. (Ozone in Water Treatment 1991).
A clear improvement in filtered water turbidity when preozonization was used in place of
prechlorination or as on alternative to no oxidative pretreatment . (Ozone as an Aid to Coagulation
and Filtration).
In one study, (Hodges 1979) reductions in filtered water turbidity were noted as soon as 20 minutes
after the ozonator was turned on. These extremely fast improvements in water clarity seem to
increase up to ozone dosages of 1.9 mg/L. (Ozone in Water Treatment 1991).
24
Mechanisms for the coagulating effects of ozone:
1) Loss of Organic Coating

Ozone strips the organic coating from clay particles returning them to their destabilized state.
These particles would be relatively free of the high negative surface charges and thick adsorbed
organic layers that serve as a barrier to particle agglomeration. Therefore the particles would
flocculate much more easily. It should be noted that this mechanism cannot account for a
significant TOC removal since only a minor fraction of the organic content in most natural waters
is associated with clay particles.
2) Increased Aluminum Complexation

Carboxylic and phenolic functional groups in natural organic matter (NOM) form complexes with
aluminum oxide surfaces, forming organic matter-aluminum surface associations. Removal of
DOC by activated alumina increased with increasing numbers of acidic groups up to perhaps an
optimum of three. Ozonation can therefore increase the degree of adsorption of NOM to activated
alumina and to aluminum hydroxide by increasing the concentration of oxygenated functional
groups (especially carboxylic acids).
3) Increased Calcium Complexation

An increase in the number of carboxylic acid groups may also lead to an increase in the degree of
calcium complexation, resulting in direct precipitation of the organic matter. An increase in the
complexation of Calcium may also lead to improved adsorption of organic to alum floc, as well as
to other precipitating metal oxide surfaces such as MnO2.
4) Organic Polymerization
Ozone induced oxidative coupling may also play a role in the coagulating effects of ozone.
Oxidative coupling involves the joining of small soluble molecules via C-C and C-O bonds to give
large fulvic acid type molecules and eventually the larger and relatively insoluble humic acid
type molecule . Oxidative coupling is thought to be responsible for the presence of nearly all
colored substances. These reactions increase the molecular size improving the removability of
organic material by coagulation.
5) Breakup of Fe and Mn Complexes

Ozone is known to be effective at breaking up certain types of organic complexes of iron and
manganese.
6) Reactions with Algae

See section of Algae removal on page 8.
Coagulation/Filtration:
In addition to the ability of ozone to immediately oxidize some organohalide precursors (TOX), it
may also improve the removal of organic precursors in subsequent coagulation. The reasons for
this have yet to be explained, however, preozonation can improve the coagulation of THM
precursors through both subsequent coagulation and filtration. (Ozone in Water Treatment 1991).
25
Ozonation Vs. Chlorination (a summary)

When a disinfectant is used in the water treatment process, it reacts with background natural
organic matter (NOM) to produce DBP’s. The health risks associated with many DBP’s are yet
to be determined, therefore, no maximum contaminant levels have been established.
With respect to chlorination DBP’s, the main concerns are with trihalomethanes (THM’s) and
haloacetic acids (HAA’s). These DBP’s are a result of chlorination and have been identified as
possible carcinogens. They are organic chemicals that appear most consistently and at the highest
contaminant levels compared to other chlorination DBP’s.
In Canada, the maximum allowable concentration for THM’s is 100 ug/L, based on running
quarterly averages. HAA’s are currently under review for possible inclusion in the Canadian
guidelines; however, the lack of data on HAA levels in Canada may delay development of a
guideline for several years. (1998 IOA PAG Annual Conference).
Although ozone DBP’s are not regulated, they will likely receive regulatory attention in the future.
When ozone is used as a disinfectant, the main by-products of concern are:
Aldehydes
-formaldehyde, acetaldehyde, glyoxyl, methyl glyoxyl, propanol, butanol, pentanol,
heptanol
Carboxylic acids
-acetate, formate, oxylate
Keto acids
-glycoxylic acid, pyruvic acid, ketomalonic acid
Bromate (if bromide is present in the raw water)
Disinfection by-products expected to be formed from chlorination include:

Trihalomethanes (THM)
Haloacetic acids (HAA)
Haloacetonitriles
Halogenated ketones
Chloropicrins
Chlorinated phenols
Cyanogen chloride
Aldehydes
26
Ozonation Vs. Chlorination
Chlorine Chemistry:
When chlorine gas (Cl2) or chlorine compounds (Ca(OCl)2 or NaClO) are added to water,
hypochloric acid (HClO) is formed. The acid dissociates into hydrogen and the hypochlorate ion
(OCl-).
Free Chlorine = hypochloric acid + hypochlorate ion (hypochlorite) + molecular chlorine
If water contains ammonia (NH3) the hypochloric acid reacts to form monochloramine
(NH2Cl).
Monochloramine may further react with ammonia to form dichloromine (NHCl2).
Dichloromine may further react with ammonia to form trichloramine (NCl3).
The formation of monochloramine, dichloromine, and trichloramine is progressive. If sufficient

chlorine is applied, the ultimate product is trichloramine until all ammonia is exhausted.
Combined Chlorine = monochloramine + dichloramine (very slow but stable disinfectants)
Trichloramine is a chloride and does not have disinfectant power.
Ozone’s Reactivity With Different Types of Chlorine:
Free Chlorine:
Under normal conditions found in water intended for potable water treatment, free chlorine is in the
form of hypochlorous acid or hypochlorite. These two species are formed from the hydrolysis of
molecular chlorine in water.
Cl2 + 2H2O HClO + Cl- + H3O+

HClO + H2O ClO- + H3O+
Like hypobromites, hypochlorites are oxidized by ozone resulting in chlorates and chlorides
ClO-  O3 ClO3- + Cl-
At a given pH, the rate of free chlorine oxidation by ozone is greater than the rate of free bromide
oxidation. e.g. 1 mg/L O3 @ pH 7 Chlorine half life = 15 min
Bromine half life = 60 min
Combined Chlorine:
Inorganic chloramines and bromamines are degraded by ozone, although the degradation rates are
not very high.
27
Parameter Chlorine Ozone

Primary Disinfection
Primary Disinfection Effective More effective
Flexibility of future Limited Good flexibility
regulations (cryptosporidium)
Possible synergy with other None Possible
disinfectants (chlorine as
residual)
Disinfection By-products
Chlorinated DBP’s Higher Lower
Bromate None Non Detect

Overall by-product risk Higher Lower
Regrowth potential
AOC Limited increase 1.5 to 3 times chlorine
BDOC No increase 1 to 6 times chlorine
HPC growth rate Same as ozone Same as chlorine
Overall regrowth No increase Ozone increases
(1998 IOA PAG Annual Conference).
28
Summary
Ozone reacts with various compounds either by a direct route involving molecular ozone, or
through, a much less selective process, involving several radical species of ozone that are formed
when it decomposes in water. It is the combination of these two processes which give ozone its
powerful oxidizing capabilities.
The fact that chlorination produces several harmful by-products, and gives water a distinct taste,
has lead to a search for alternative methods of drinking water disinfection, with ozone being one of
the most frequently mentioned choices. The disinfection rate of ozone is much greater than that of
chlorine. In fact one report The Technology of Ozone in the Oxidation of Organic Compounds
stated that the disinfection rate of ozone is 3,125 times faster than that of chlorine.
Ozone is also effective at killing algae, and removing reduced iron, manganese, and hydrogen
sulfide which give water unpleasant taste and odors.
The organic material in water (e.g. decaying vegetation) is also quite susceptible to ozone
oxidation. It is the oxidation of this material that leads to much clearer water, giving ozone its
reputation as an effective bleaching agent . This process involving the removal of organic
constituents, which can also give water taste and odors, can be further enhanced through post
ozonation filtration.
With the ever increasing demand for cleaner water many new compounds are under review and
may become part of the Canadian Standards for Domestic Consumption. Trihalomethanes
(THM’s) form one group of chlorination by-products, which can be reduced by pretreatment of
ozone.
There are however by-products which can form as a result of ozonation. Although the processes
are not yet fully understood, the by-products of ozonation are generally regarded as being less
harmful than the by-products of chlorine disinfection. The degree, to which these by-products are
formed, if at all, depends on the characteristics of the untreated water.
In general the compounds of the most concern (aldehydes, carboxylic acids, and keto acids) which
are produced upon ozonation are readily biodegradable if passed through granular activated carbon
(GAC). Standards for these compounds have yet to be set for Canadian drinking waters, however,
if Canada adopts standards similar to the U.S. then post GAC adsorption would generally meet the
required concentrations. It is the presence of the bromate ion (BrO3-) which remains the sole
deterrent to even more rapid acceptance of ozone as a water treatment technology.

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Ozone Reactions with Common Water Quality Parameter

900 Major Bennett Dr.

Ozone Reactions with Common Water Quality Parameters

Disinfection By-Products of Ozonation

Primary Effects of General Disinfection By-products Formation

Preozonation Effects of Other Treatment Processes

Ozonation Vs. Chlorination

AOC: Assimilable Organic Carbon

Techniques For Proper Removal Following Ozonation

Problem / Parameter Reaction Product Removal Process

Sulfide (rotten egg smell)  Sulfate Straight ozonation effective

Iron (taste, staining)  Iron Oxide Post-filtration required to

Manganese (taste, staining) Manganese Oxide Post-filtration required to

Smaller more biodegradable Post-filtration through GAC

Ozone Reactions With Common Water Quality Parameters

These two properties of ozone enable it to react in three ways:

Iron & Manganese:

Iron & Manganese Oxidation:

Disinfection & Ozonation:

Table 1 CT values for common disinfectants for 99% inactivation at 5oC

Bactericidal efficiency of Ozone at Neully-sur-Marne Plant

Cryptosporidium causes cryptosporidiosis if ingested, an intestinal disease which makes healthy

CT values for disinfectants to inactivate 99.9% (3 logs) of Giardia lamblia cysts

CT Levels of Ozone for 99% Inactivation of Cryptosporidium and Giardia

C. parvum 1.0 5 and 10 5-10

C.baileyi 0.6 and 0.8 4 2.4-3.2

C. parvum 0.44 6 2.6

G. lamblia (Giardia) 0.11-0.48 0.94-5 0.53

G. lamblia 0.03-0.15 1.06-5.5 0.17

Ozone N. gruberi 0.70 ---

Free Chlorine N. gruberi 27 3857%

Chlorine Dioxide N. gruberi 5.51 786%

Reactions with aquatic humic substances:

Non volatile ozonation products derived from humic substances include:

Reactions with Synthetic Organic Chemicals:

Micro pollutants and their reactivities with ozone

Alkenes Slightly reactive

Alcohols, Ethers, Aldehydes, Esters and Carbonyl groups Unreactive

Aromatic Compounds Possessing OH or NH2 group Reactive

Possessing NO2 or Cl group Much less reactive

Phenols and derivatives Strongly reactive (Initial

Amines and derivatives Strongly reactive (produces

Pesticides Chlorinated organic Slowly reactive

Herbicides Phenoxyacetic Strongly reactive

Surfactants (chief active Not readily oxidized

Dyes (related to the presence of Strongly reactive

Tastes and Odor:

Treatment Average Taste Threshold Flavor Reduction (%)

Turbidity: (Particulate removal)

Reduced Non-metal species:

Species Concentration of Ozone Half life (minutes)

Maximum Acceptable Levels in Water Used for Domestic Consumption

General Ozone Reduction Efficiency

Iron Very Effective (Effectiveness reduced with high levels of organic

Manganese Effective after the removal of Iron has occurred (Effectiveness

Turbidity Very effective (when post-ozonation-filtration is used)

Coagulation Greatly improves coagulation / filtration efficiencies

Algae Effective, but species dependant

General Disinfection Very Effective

Bacteria (E.Coli, Salmonella, & Very Effective

Giardia Effective, when a residual ozone concentration is produced

Cryptosporidium Effective (contact time more relevant than residual ozone

Amoeba Cysts (Naigleria Very effective

TOX (total organic halides) Effective