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Water and wastewater disinfection with ozone: A

critical review
a b
Riley N. Kinman & G. Rempel
a
University of Cincinnati , Cincinnati, Ohio
b
Waterworks, Waste and Disposal Division , City of Winnipeg, Manitoba, Canada
Published online: 09 Jan 2009.

To cite this article: Riley N. Kinman & G. Rempel (1975) Water and wastewater disinfection with ozone: A critical review, C R
C Critical Reviews in Environmental Control, 5:1, 141-152, DOI: 10.1080/10643387509381625

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 WATER AND WASTEWATER DISINFECTION WITH OZONE: A CRITICAL REVIEW

Author: Riley N. Kinman

University of Cincinnati
Cincinnati, Ohio

Referee: G. Rempel
Waterworks, Waste and Disposal Division
City of Winnipeg
Manitoba, Canada
Downloaded by [Cornell University Library] at 18:25 19 November 2014

INTRODUCTION tion by 2 years, since chlorine disinfection of a

Disinfection of water and wastewater is one of
the most important unit processes involved in the
treatment system. Whether the particular water is
to be used for potable purposes or to be dis-
charged to the environment, the goal of disinfec-
tion is to destroy pathogenic organisms. Chlorine
in one of its many forms has been used for many
years to accomplish this destruction of pathogenic
organisms and today accomplishes a preventative
medicine job surpassing all of the shots and
medicines administered by medical people.
Chlorine is the most widely used water disinfect-
ant in the world today. In spite of all the success
attributed to chlorine, there are problems en-
countered in its use in certain disinfection applica-
tions. These problems have led to the search for
new and better disinfecting agents. Ozone is one
such agent which has received considerable atten-
tion in the field of research in recent years.
Ozone is not new to the water disinfection
field. Some experimental plants using ozone as the
water disinfectant were in use as early as 1892.1
The first really important plant was put in service
in Nice, France, in 1906 and is still in service.
Thus, ozone predates chlorine for water disinfec-
municipal water supply was initiated in 1908.' 7
Ozone has never been a serious competitor for
chlorine over the years, even though some French
engineers have called ozone the water disinfectant
of choice. There are many reasons for the lack of
use of ozone in disinfection applications. These
reasons are related to the advantages and disadvan-
tages of ozone when used as a disinfecting agent as
shown in Table 1.
Careful review of the advantages of ozone
indicates why considerable work is underway to
see if the disadvantages can be overcome to such a
degree that ozone may be utilized for various
disinfection applications.
Figures 1 and 2 contain various flow schemes in
which ozone or a combination of ozone plus
chlorine serve as the disinfecting agent. There are
many possible uses of ozone in a treatment plant
other than disinfection. Chemical oxidation, pre-
treatment for various kinds of organic removal,
and odor control are valid uses to which ozone
may be put. Most of the plants now using ozone
for potable water disinfection use it as a pretreat-
ment followed by chlorine. Even a wastewater
plant in Florida2 using ozone plus sonication for
disinfection must also add chlorine in order to be

January 1975 141

 TABLE 1
Advantages and Disadvantages of Ozone for Disinfection Applications
Advantages
Wide spectrum disinfectant
Has high oxidation potential
Oxidizes taste and odor causing compounds
Removes color from water
Adds oxygen to water
Lowers BOD and COD values
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Low concentrations are adequate
Does not form noxious compounds in treated water
as far as is known
Avoids problems associated with transportation of
potentially harmful chemicals
in compliance with state regulations. Many engi-
neers and scientists are looking at ozone as a
potential replacement for chlorine, which has been
in short supply recently in some locations and is
coming under fire in other locations because of the
potential toxicity of some of the chlorination
reaction products. Review of key recent technical
literature on ozone research brings the "State of
the Art" into focus.
RECENT TECHNICAL LITERATURE
ON OZONE FOR DISINFECTION
Disinfection Efficiency
Broadwater, Hoehn, and King3 selected three
bacterial species, Escherichia coli, Bacillus cereus,
and Bacillus megaterium, to determine the mini-
mum lethal concentration of ozone when a 5-min
contact period was used in a pure water system.
Spores of B. cereus and B. megaterium were
studied under the same conditions. The authors
found the organisms to be sensitive to ozone with
death of all vegetative cells caused by 0.12 mg/1 for
B. cereus and 0.19 mg/1 of ozone for B.megate-
rium and E. coli. Spores of B. cereus and B.
megaterium were equally resistant to ozone. The
O 3 dose required to destroy all the spores in 5 min
142 CRC Critical Reviews in Environmental Control
Disadvantages
High capital cost for equipment
Must be generated at the site
High reactivity results in low selectivity
Low solubility under normal conditions
Operation and maintenance may be a "headache"
Residual O 3 cannot be maintained in H2 O for long
time periods
More expensive than chlorine at present
Standby chlorinator may be necessary
Measurement is difficult
May not oxidize certain organics to CO2 and H, O in
disinfection process
was between 2.03 mg/1 and 2.29 mg/1. The spores
were much more resistant to the applied ozone.
The authors mentioned the often described "all
or none" die-away phenomenon associated with
ozone. It is hard to believe that the application of
even minute concentrations of ozone do not have
some effect on die-away of organisms. This author
believes that a demand for ozone is exerted by
some trace contaminants in the system which
causes decomposition of the ozone before it can
come in contact with the organisms and react with
them. Ozone decomposition may occur very rapid-
ly (in microseconds) in the presence of even
minute quantities of trace reducting agents, cata-
lysts, and metallic ions. Demand for ozone caused
by these materials would increase the cost of
ozonation in a practical disinfection situation.
Ozone demand vs. organism die-away is a consider-
ation that should be carefully evaluated when
ozone is under consideration for a given water
disinfection application. The so-called "all or
none" die-away phenomenon often observed in
ozone disinfection work is caused by ozone
demanding substances in the system.
Katzenelson et al.4 studied the action of ozone
on E. coli, coliphage T 2 , and Polio virus I at 5 °C in
pure systems. Concentrations of ozone from 0.07
 Ozone Disinfection
(
a. N
Raw
1,
Screening Coagulation Filtration Distribution

Ozone, .Chlorine

b.
Raw
H2O
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Screening Coagulation Filtration Distribution

/Chlorine
Ozone* *Dechlorinate

»{
Screening Coagulation Filtration Distribution

, Chlorine

d.
Raw
H,0
1,
Screening Coagulation Filtration Distribution
FIGURE 1. Ozone Disinfection Flow Schemes for Potable Water Disinfection.

mg/1 to 2.5 mg/1 were used in the polio inactiva-
tion studies. They reported that they were unable
to determine the exact time for 99% inactivation
of Polio virus type I, but that the time was less
than 10 sec at 5°C and pH 7.2 with O 3 concentra-
tion up to 2.5 mg/1 in the pure system. E. coli and
coliphage T2 were more sensitive to the ozone
than the Polio virus. Rapid rate of kill is a
characteristic of ozone witnessed by many work-
ers.
Majumdar, Ceckler, and Sprouls studied the
disinfection efficiency of ozone with Polio virus.
The objective of this study was to "delineate the
basic mechanism of inactivation of Polio virus I by
ozonation. Specific investigation,5 including both
batch and continuous flow experiments, were
carried out to determine the rate equations of
Polio virus inactivation with respect to contact
time and ozone concentration in triple distilled
water and primary and secondary wastewaters."
This study represents a good attempt to better
understand the relationship of ozone concentra-
tions, contact time, and virus inactivation. An
attempt was made to hold the ozone concentra-

January 1975 143

 0 Ozone
a. i
Raw
Wastewater
i
Pretreatment Activated sludge or Disinfection Receiving
trickling filter process water

•Ozone
b. \
Raw
Wastewater
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Pretreatment Physical-chemical Disinfection Receiving

process water

s Ozone
/Ozone
c.
\
Raw
Wastewater
I,
Pretreatment Physical-chemical Disinfection Receiving
process water

Ozo ne+sonication
d. ^Chlorine
Raw
Wastewater

Pretreatment Physical-chemical Disinfection Receiving

process water
FIGURE 2. Ozone Disinfection Flow Schemes for Wastewater Disinfection.

tion constant throughout the 8-min- contact time
and this was accomplished within a reported
±7.2%. Since the ozone concentration in water or
wastewater after some dose has been applied
changes constantly, this was and is a formidable
task. The authors are to be commended for their
efforts in this respect.
Several aspects of this study should be carefully
considered, or a too-liberal interpretation of the
conclusions may result. The authors state, "Ingols
et al.2 concluded that the bacterial action of
chlorine occurs in a progressive fashion, whereas
that of ozone is sudden after the threshold value is
reached."* Use is made of the term threshold
value for virus inactivation by ozone. This term
may be misleading if the user does not clearly
explain what the term means. A dictionary defini-
tion of threshold is the point at which a physio-
logical effect begins to be produced. Conclusion
number one of this study was given as: "A

*The authors cited reference 6, which is the wrong one; reference 7 is the correct article by R. H. Fetner and R. S. Ingols.

144 CRC Critical Reviews in Environmental Control

 threshold concentration of ozone exists for inacti-
vation of Polio virus. Based on the findings of
inactivation studies in triple distilled water, the
threshold value may be taken as 1.0 mg/1."
If the assumption is made that the threshold
effect meant here is 99% or 995% inactivation of
the viruses at a concentration of 1.0 mg/1 ozone,
the impression given is. that 1.0 mg/1 ozone will
assure the same level of virus inactivation in a
water or wastewater under actual disinfection
conditions. This is not so. No concentration of
ozone can guarantee any level of virus inactivation
unless other water quality conditions are met.
Perhaps if the suspended solids level were 0 some
level of virus inactivation could be assured by an
ozone concentration of 1.0 mg/1. Whether the level
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of inactivation would be 90%, 99%, or 99.9%, or
some other percentage would depend on the ozone
demand and the nature of substances in the water
other than the viruses, and the physical state of
the viruses.
Conclusion 2 of this work was, "the relation-
ship of the ozone concentration and the contact
time with the survival of Polio virus may be
expressed by the following:
0.18S-°-*6 C < 1.0 mg/1
0.13S-°- 36 C> 1.0 mg/1
It is therefore, concluded that two distinct rate
mechanisms exist, one above and another below
the threshold concentration, 1.0 mg/1."
Careful review of the conditions under which
these simplified equations were developed from
the rate equations should be made before these are
applied to the design of a full scale system.
Ozone disinfection literature is filled with
statements presented as fact that ozone can be
substituted for chlorine, the wastewater disinfect-
ant presently in use, as if O 3 has been used as the
disinfectant full scale with complete success on
municipal effluents. This is not the case. Most of
the U.S. data concerning the efficiency of O 3 as a
wastewater disinfectant have been generated on
either pilot scale or bench scale, yet notice the
opening paragraph from the work of Nebel et al.8
"Ozone disinfection of municipal secondary
effluents offers many advantages over the use of
chlorine. A degree of tertiary treatment, removal
of suspended solids (SS), ease and safety of
operation, and an effluent that is completely safe
to the receiving stream are among the advantages
obtained at no additional cost above the cost for
disinfection. The earlier laboratory results
prompted investigations on a larger scale."
The scale of these studies varied from 0.75 to
4.0 gpm (2.84 to 15.2 1/m) which is a long way
from any sizeable municipal treatment plant. It is
unfortunate that some of those who are pushing
O 3 as a replacement for chlorine in wastewater
disinfection do not maintain objectivity in their
presentation of the data they generate. For ex-
ample consider the statement in the opening
paragraph concerning suspended solids removal by
O 3 . Nebel et al.8 indicated that O 3 removed (SS).
This is just not so. Their Figure 8, which is a plot
with suspended solids, mg/1 as the y-axis and dates
as the x-axis titled "Figure 8 — Suspended Solids
Reduction by Ozonation" is misleading. If a study
is made of the figure, O 3 alone received credit for
the suspended solids removal. In reality a floata-
tion process was used to remove the SS as a froth.
Later in the article the statement is made, "If
ozone is applied properly to a secondary effluent,
it can be used to remove suspended solids by a
floatation process that utilized skimming devices
to remove solids as a froth." No mention is made
that the froth is caused by an oxygen-ozone
mixture which consists of 97% oxygen and 3%
ozone.
Other statements further confuse the issue.
Such statements as "This implies that the mech-
anism of virus inactivation and bacterial kill may
be different for ozone, or it may be simply a
reflection of the fact that ozone is twice as
powerful an oxidant as chlorine." If the authors
are implying that ozone has a much higher
oxidation potential than the chlorine species pres-
ent in water, this is true, but the oxidation
potential of O 3 -2.07V at 25°C is not twice that
of hypochlorus acid, HOC1, which is the impor-
tant chlorine species in disinfection with chlorine.
Important chlorine species oxidation potentials are
as follows:
Chlorine species in H3 O Oxidation potential at 25° C
HOC1 -1.49 V
NHjCl -0.75 V
CL, -1.36 V
O3 does have a high oxidation potential, but
not twice as high as the chlorine oxidation
potential. Ozone's oxidation potential is twice as
great as the oxidation potential of monochlora-
mine. Other statements sound more like a "sales
January 1975 145
 pitch" than fact. Consider the following, "The
literature shows that ozone brings about disinfec-
tion 3,100 times faster than chlorine."8 All kinds
of questions could be raised as to how such a
determination was made and whether any signifi-
cance can be attributed to such a statement.
Hypochlorus acid is known to destroy many
organisms in water in 30 sec or so. If one looks at
the aforementioned statement as follows:
1/3,100 X 30 sec = 0.0097 sec
This is an extremely short time. Measuring kill of
organisms at this short time does not appear
technically feasible. Such a comparison of ozone
with chlorine is misleading at best and does not
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contribute to a better understanding of the disin-
fection process.
Nebel et al.9 conducted a pilot plant study at
the Fort Southworth Sewage Treatment Plant in
Louisville, Kentucky to determine if a 15 mg/1
dose of ozone would meet the disinfection require-
ments for a larger plant. An 80 gpm package
activated sludge plant was used to provide a
secondary treated effluent which contained a large
quantity of industrial waste. A dose of 15 mg/1 of
ozone was applied to this effluent with a contact
time of 22 min in an over-under baffled contacter
during the 6-week-study. Disinfection results were
presented as the average of 12 individual millipore
filter analyses.
Fecal coliform levels were reduced from a range
of 52,000 to 854,000/100 ml in the influent to a
range of 19 to 798/100 ml in the effluent from the
contact chamber. Fecal Streptococci levels were
reduced from a range of 0 to 8,000/100 ml to a
range of 0 to 130/100 ml in the effluent. Total
coliform levels were reduced from a range of
400,000 to 9,150,000/100 ml to a range of 47 to
2,703/100 ml in the effluent. No attempt was
made to vary the ozone dose throughout the
six-week-study.
Four samples were collected and submitted to
the EPA Taft Center for virus assay. The data
indicated such a large reduction in virus levels after
the secondary pilot plant (nine hr detention in
aeration tank) that the reductions attributable to
ozone disinfection were not significant. Only 2
PFU/gal(plaque-forming units per gallon) remained
after the secondary treatment. No virus was found
in the samples taken after ozonation.
146 CRC Critical R eviews in Environmental Control
A study was carried out with f2 bacteriophage
utilizing doses containing 100 billion plaque-
forming units/ml innoculated into the secondary
effluent. Samples were taken every ten sec at the
top of the first chamber of the contact unit and at
other chambers in the unit. Total inactivation of
the f2 phage occured after a contact period of
approximately five min with the 15 mg/1 ozone
dose.
Significant reductions in BOD5, COD, color,
and turbidity were noted. These reductions aver-
aged about 15% for BOD S , 29% for COD, 79% for
color, and 70% for turbidity. Total organic carbon
levels were not appreciably affected by the 15
mg/1 dose of ozone in this municipal secondary
treated wastewater.
The authors9 concluded that "The pilot study
has demonstrated that ozone can be successfully
employed as an alternative to chlorination for
rapid disinfection and concurrent tertiary treat-
ment of combined municipal-industrial secondary
effluent. In most instances, earlier laboratory
results have been equalled or surpassed. Ozone
brings about effluent quality improvement by a
combination of direct oxidation and an ozone-
induced flotation process. An ozone contact cham-
ber of simple design allows efficient ozone transfer
and froth removal without extensive pumping or
mixing operations. The ozonized effluent is non-
toxic, high in dissolved oxygen content, and of a
visual quality as to make it indistinguishable from
potable water."
Some key comments are in order regarding this
study. It was a relatively short-term study. Six
weeks is not a long time period for study of a joint
municipal-industrial wastewater. The effluent from
the secondary package plant was not a typical
effluent in that most conventional activated sludge
plants do not provide for nine-hours-detention
time in the aeration basin. A dose of 15 mg/1
ozone is a large amount of ozone or any other
disinfectant for that matter. These comments
indicate that the author's conclusions may not
have a firm basis in fact. Much more work must be
carried out before the conclusions as stated can
have a firm data base.
Zenz and Weingardner1 ° studied the ozonation
of microstrained secondary effluent. Primary ob-
jectives of this study were to determine if ozone
disinfection would provide effluent levels of fecal
coliform, total coliform, and fecal streptococcus
which would meet the standards for these organ-
 isms in Illinois, and determine the costs required in
the process. In addition to these two primary
objectives, the authors were interested in the
effect of ozone on other parameters of water
quality. Measurements were taken to determine
the reductions in color, turbidity, cyanide, phenol,
nitrites, and ammonia which could be attributed
to ozone disinfection of the effluent from the
secondary microstrained 90 gpm pilot plant. An
ozone contact time of about 15 min was provided
in two-30in.-diameter contactors. The authors
reached the following conclusions:
1. Ozone is a very effective bactéricide.
Above an ozone dosage of 6.0 mg/1, fecal coli-
forms, total coliforms, and fecal streptococcus are
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virtually eliminated.
2. There is a definite reduction in BOD from
ozonation in the order of 30%. This could be
applicable in cases where third-stage filters cannot
reduce BOD to the 4 to 5 ppm range, because of
the presence of soluble BOD.
3. Ozone treatment produces a striking re-
duction in color.
4. Above dosages of 6 mg/1 there was found
to be a modest but constant reduction in effluent
turbidity.
5. Reductions in cyanide, phenol, and ni-
trites were also noted. No reduction in ammonia
was observed.
6. No detectable ozone residual in the efflu-
ent was observed. It is assumed that the ozone
quickly reacted with the organics in the effluent.
7. The ozone demand by tertiary effluent
appears quite high and ranges up to 6 mg/1.
8. The electrical costs for ozonation re-
quired to achieve Illinois bacterial standards were
high for the pilot unit tested as compared to
equivalent chlorination costs. However, the costs
presented for ozone are an estimate only and for a
larger plant these costs would probably be lower.
9. A cost analysis of the process was made.
It was found that the electrical operating costs for
the pilot installation amounted to 1.74^/1,000 gal.
These conclusions are not out of line with what
others have found under similar conditions. Two
of the conclusions have considerable bearing on
the potential use of ozone for disinfection applica-
tions in this country. Conclusion 7 relating to
ozone demand is very important. Ozone will
always have a higher demand that chlorine under
the same conditions. Put in another perspective
the authors indicated that 3.0 mg/1 chlorine would
accomplish the same disinfection as the 6.0 mg/1
ozone. The demand for ozone was much higher
than the demand for chlorine, so if disinfection is
the desired goal, then it appears the chlorine has a
considerable edge over ozone. Of course, if other
considerations are applied in the analysis, then the
edge that chlorine has over ozone may not appear
as great.
Conclusions 8 and 9 are extremely important
and require a careful look at their basis. The
authors were careful in determining the power
used to provide the ozone for this study. Watt-
meters were installed to measure power consump-
tion related to ozone production and distribution.
The following figures revealed what it cost them to
generate ozone.
Total Electrical Operating Costs
Air blower cost 0.04^/1,000 gal
sewage treated
Desiccator cost 0.35^/1,000 gal
sewage treated
Pumping cost 0.80^/1,000 gal
sewage treated
Ozonator cost 0.55«S/l,000 gal
sewage treated
Total 1.74^/1,000 gal
sewage treated
These costs do not include capital costs or
maintenance costs. Electricity cost was taken as
0.8^/kilowatt-hour. Even if the assumption was
made that a scaled-up plant would have cheaper
ozone, comparison with the cost for providing
chlorine would show that chlorine is considerably
cheaper. Comparable costs for chlorine disinfec-
tion in this study were given as 0.25^/1,000 gal
treated. Sodium hypochlorite was assumed at a
cost of 10^/lb of chlorine. Using these comparable
numbers of 1.74^/1,000 gal treated for ozone, and
0.25^/1,000 gal treated for chlorine, the ratio is
almost 7:1 in favor of chlorine. Even with the
knowledge that cost is not everything, it is no
surprise that disinfection with ozone has been slow
to gain acceptance. Many of the advantages
claimed for ozone disinfection are not amenable to
a cost vs. benefit analysis. The same would apply
for disinfection with chlorine. Hence, only hard
costs (costs for electricity or chemical cost of
chlorine, etc.) can readily be determined. Energy
consumption and energy costs are on everyone's
mind. Costs will continue to be a major decision-
January 1975 147
 making parameter in disinfection applications in TABLE 2
this country. Expense may well slow the accept-
ance of ozone in many installations. Selected Log Kills Taken from the University of Notre
Dame Data in the Sonozone Brochure (January 24,1974)
One of the newest proposed package systems
for use of ozone in wastewater treatment is called O 3 — Pseudomonas
the "Sonozone" process.2 This packaged process fluorescens Sonozone
uses a complex physical chemical process of log org/ml log org/ml
tertiary treatment followed by ultrasonics and
ozone. In the first large-scale plant at Indian Kill Time Kill Time
Town, Florida, dedicated on May 3, 1974, effluent 2 log 30 sec 2 log 20 sec
from an old trickling filter plant is treated in a 6 log 1 min 6 log 35 sec
plant designed for 570,000 gal/day. Sewage is . 0 out @ 1 min 30 sec 0 out @ 1 min
subjected to coagulation, flocculation, and settling
with ferric chloride used as the coagulant. Filtra- O 3 — Escherichia coli Sonozone
log org/ml log org/ml
tion by pressure sand with added polymer follows
the coagulation process. Final treatment consists Kill Time Kill Time
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of ozonation and ultrasonics. Sludge is dried on

sand drying beds with the water returned to the 2 log 10 sec 2 log 8 sec
process. Such a complex treatment plant should 6 log 40 sec 6 log 17 sec
produce an effluent of high quality. 0out@ 1 min 15 sec 0out@ 30 sec

On the day of the dedication the plant was O 3 - Shigella Sonozone

suffering from foam problems plus carry-over of log org/ml log org/ml
solids from the stages of the process ahead of the
Kill Time Kill Time
ozone and sonics section from which the process
gets its name. This points out one of the problems 2 log 15 sec 2 log 10 sec
in the use of ozone which is true for any 6 log 40 sec 6 log 22 sec
disinfectant. Disinfection by any means other than 0 out @ 1 min 15 sec 0 out @ 45 sec
radiation or heat cannot be substituted for other
treatment units in the plant. If the solids removal O 3 —Salmonella
typhimurium Sonozone
portions of the plant fail, then the disinfection log org/ml log org/ml
step will fail to provide a completely virus-free
effluent no matter what the manufacturer claims. Kill Time Kül Time
Effluent from such a plant could be expected to
contain bacteria and virus even though a heavy 2 log 15 sec 2 log 10 sec
6 log 45 sec 6 log 30 sec
dose of ozone was applied. Disinfection, whether
0 out @ 1 min 15 sec 0 out @ 1 min
applied by ozone or ozone plus ultrasonics or
chlorine; is not a panacea for all kinds of failures O 3 — Staphylococcus
in the treatment process units proceeding the aureus Sonozone
disinfection step. log org/ml log org/ml
It is useful to look at the laboratory data Kill Time Kill Time
supplied in the Sonozone brochure for kill of
various microorganisms by ozone only and sono- 2 log 20 sec 2 log 10 sec
zone. Dr. Morris Pollard at the University of Notre 6 log 1 min 7 sec 6 log 45 sec
Dame, South Bend, Indiana, directed the labora- 0 out @ 2 min 0 out @ 1 min 15 sec
tory comparisons for ozone and sonozone on the
o3- Vibrio cholorae Sonozone
following organisms: Escherichia coli, Pseudo- log org/ml log org/ml
monas fluorescens, Shigella, Salmonella typhimur-
ium, Staphylococcus aurais, and Vibrio cholorae. Kill Time Kill Ti
On June 14, 1974, the following data for compar-
able test conditions in the Sonozone brochure were 2 log 20 sec 2 log 10 sec
6 log 30 sec 6 log 13 sec
reported. Ozone dose applied was not given. 0out@ 45 sec Oout @ 30 sec
Table 2 contains the times picked from the

148 CRC Critical Reviews in Environmental Control

 brochure for various log kills. Ozone alone had a
minimum kill time of 10 sec for a 2-log drop,
while sonozone had a minimum time of only 8 sec
for the 2-log drop. Ozone alone had a maximum
kill time of 30 sec for a 2-log drop, while sonozone
had a maximum time of 20 sec for the same 2-log
drop. To provide a 6-log drop, ozone alone had a
minimum time of 30 sec while sonozone had a
minimum time of approximately 13 sec for a 6-log
decrease in the number of surviving organisms.
Ozone had a maximum time of 1 min 7 sec
approximately for a 6-log drop while sonozone
had a maximum time of 45 sec for the same 6-log
decrease in surviving organisms. Complete kills for
ozone only occurred in under 2 min for all
organizms tested, while complete kill for the
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sonozone occurred in under 1 min 15 sec for all
organisms tested. From these data it is difficult to
see any real justification for adding ultrasonics to
the ozone. Ozone alone killed the organisms in a
time fast enough for most contact chamber de-
signs. Additional data on viruses may indeed
indicate that ultrasonics plus ozone are necessary
for complete virus destruction, but the data to
date do not indicate that the ultrasonics contri-
bute necessary additional improvement in the
ozone disinfection efficiency.
Kinman1 ! reported that O 3 is a powerful
disinfecting agent in water or wastewater and is
more independent of pH effects or temperature
effects than iodine or chlorine when in contact
with organisms in wastewater. In these studies
carried out at 1°C and above, in simulated poorly
treated and well treated effluents, O 3 destroyed
coliform organisms, total bacteria, and fecal strep-
tococci more rapidly than either chlorine or
iodine. Temperatures from 0°C to 10°C were used
to simulate cold weather conditions. Wastewater
pH was varied from pH 7.0 to pH 9.O. Destruction
TABLE 3
Destruction of Total Coliform in 20% Raw Park Hills, Kentucky Sewage at pH 7.0
and 1°C by Ozone
Total Volatile
Run solids solids
7/19/73 1,083 mg/1 175 mg/1
of the organisms was rapid at all pH values and
temperatures studied. Little difference in rate of
destruction was noted between 0°C to 2°C, 5CC,
7°C, 20°C or 30°C for total bacteria. Table 3
contains data for destruction of total coliforms at
pH 7.0 and 1.0°C in a simulated poorly treated
effluent. Note that greater than 99% kill occurs
within the first minute in this simulated poorly
treated effluent.
Ozone Disinfection Technology
Rosen12 described some of the gas generation
technology which is presently available for the
application of oxygen and ozone to wastewater.
Since cost is one of the problems associated with
ozone disinfection of wastewater, any process
which will assist in reducing costs is important to
the success of ozonation. Ozone production costs
can be lowered if oxygen is available at a cheap
enough cost to warrant its use. Liquid oxygen
aeration systems were described in this paper with
considerable cost information. Effort was made to
show the advantages for ozone if such a liquid
oxygen system is in use. There is no question that
if part of the capital costs associated with the
oxygen production facility can be assigned to the
other treatment units, then the costs of ozone
production decrease. Also, higher ozone produc-
tion efficiencies are possible if oxygen is used in
the production of the ozone rather than air. Most
of the liquid oxygen plants of any size are either
on the drawing boards or they are still under
construction. Little data exists for full-scale appli-
cation of liquid oxygen to wastewater treatment.
Several plants will be generating a great deal of
data in a few years.
Considerable explanation was given by Rosen12
of the types of ozone generating apparatus avail-
able. Advantages of one type over another were
Time Organisms
(tnin) 100 ml %Kill
3.46 mg/1 0 39,600,000 0.0
1 100,000 99.74
5 100,000 99.74
10 100,000 99.74
20 100,000 99.74
1.03 mg/1 30 10,000 99.97
January 1975 149
 presented. Ozone generator capital costs where air
is used in the generator were shown to be more
than twice the values obtained when oxygen was
used to generate ozone. Considerable details for
each of the types of ozone generators were
presented as well as schematics of the various
components necessary for a given type of ozone
disinfection facility.
Contactor design criteria were considered in
some detail. Since contact between the organisms
to be destroyed in the wastewater and the ozone
must be accomplished, contactor design is one of
the problem areas in use of ozone for disinfection.
The statement was made that, "There is much
room in this area for chemical engineers to apply
their expertise to designing specific contact sys-
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tems for the application of ozone to wastewater."
Environmental engineers have been working for
some time to develop new contacting systems for
ozone in wastewater and these attempts have not
greatly improved the overall efficiency of ozone
transfer in the disinfection process. Most of the
existing contacting systems lose considerable
ozone from the disinfection process or they add
materially to the capital and operating costs for
disinfection. Much remains to be accomplished in
the contacting process for ozone disinfection.
The concluding paragraph of this article was as
follows:
"Advanced technology for economical oxygen and ozone
generation is now available. Some systems for its applica-
tion have been developed and demonstrated. However,
only the surface has been scratched in the development of
application technology, not only in the municipal area,
but in industrial-water pollution control."
Just; what the author means by "economical
oxygen and ozone generation," is not known.
Certainly, the use of ozone at this time for
wastewater disinfection will cause an increase in
capital and operating costs over the use of gaseous
chlorine for the same purpose. In some tertiary
treatment applications the reclaimed water may be
worth whatever cost is necessary to reclaim it, but
for the average wastewater treatment plant, the
additional costs associated with ozone disinfection
may cause the management-consultant team to
select chlorine disinfection equipment rather than
ozone equipment after all other considerations are
reviewed. Each wastewater treatment situation
requires a thorough study of the receiving water
requirements and regulatory agency requirements
150 CRC Critical Reviews in Environmental Control
before the final decision can be made either for or
against ozone as the disinfectant. Also, the selec-
tion of the type of disinfectant to be applied
cannot be made without due consideration of each
of the unit processes to be employed ahead of the
disinfection step.
Nebel, Unangst, and Gottschling13 evaluated
various mixing devices for ozone dispersion in
water. Objectives of this study were to evaluate
several different mixing devices for mixing ozone
into the water or wastewater in question. Obtain-
ing solution of ozone into the aqueous solution to
be disinfected is one of the major problems
associated with its use. Large contact chambers
have been used in the past for large volumes of
water or wastewater to be disinfected and these
contact chambers result in major capital expendi-
tures in the ozone process. A more efficient
method for solubilizing the ozone would favor its
use in many treatment plants. The devices evalu-
ated in this study were specifically:
1. Static mixer element
2. ISG Mixer element
3. Sonic mixer
4. Venturi mixer
5. Porous plastic diffuser
A solution of phenol in water was used to
determine the efficiency of transfer of the quan-
tity of ozone actually obtained in the water.
Decrease in phenol concentration was equated to
ozone solubilization. The highest concentration of
ozone obtained was 4.25 mg/1 in distilled water.
This illustrates one of the major problems in ozone
disinfection. A concentration of O3 in water or
wastewater much above this value (4.25 mg/1) is
extremely difficult to obtain in a single pass
system. Chlorine concentrations many-fold higher
are easy to obtain.
The authors concluded that mixers must be
matched to the specific ozone application under
consideration. Each mixer had certain advantages
when used in a particular application, but one
mixer might be more expensive than another in
the same application. The Static Mixer was
deemed to be most promising of the mixers
studied, even though its operation is limited to low
dosage levels. This particular mixer had a high
ozone transfer efficiency. Higher dosages would
probably require multiple passes of the liquid
through the mixer.
 Mixing of the ozone into the liquid to be
disinfected is one of the major design factors and
cost factors facing the engineer who plans to use
ozone. Considerable research should be directed at
improving ozone gas transfer devices used in water
and wastewater disinfection.
Ozone Measurement
Kinman14 reviewed the problems associated
with measurement of O3 in water and wastewater:
1. Ozone loss from aqueous solution to the
atmosphere above the solution.
2. Reaction of O3 with trace constituents in
the water.
3. Ozone decomposition in the water.
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Speed of measurement is important to mini-
mize the errors involved in O 3 residual measure-
ment. Amperometric titration in some fashion
appears to be the fastest and best method for O 3
residuals in the 0 to 4.0 mg/1 range in water.
Accurate measurement of O 3 residuals in water is
an important consideration for the long-range
development of O 3 for water and wastewater
disinfection.
Ozone Toxicity
Hazucha et al. 15 studied the effects of short-
term exposure of ozone to men. The authors used
two groups of healthy young nonsmokers and two
groups of healthy young smokers to study the
effect of ozone on pulmonary function. These
groups were exposed for two hr at two dose levels
of ozone. Light exercise was performed at inter-
mittent periods during exposure to 0.37 ppm and
0.75 ppm ozone for 2 hr in order to double the
minute ventilation. Ozone concentration was mon-
itored continuously by three coulometrie-type
ozone meters. They found that the total lung
capacity was not significantly affected by the
exposure, but the residual volume increased. This
indicated an early effect in the small airways. They
concluded that a concentration of 0.37 ppm ozone
for a period of 2 hr is unacceptably high if
impairment of pulmonary function is to be
avoided in a normal, active population.
Ozone like any toxic gas should be treated with
respect. Even small concentrations for relatively
short time intervals should be avoided if possible.
Operating personnel should be informed of the
potential harmful effects of inhaling ozone.
SUMMARY
Review of the recent pertinent technical litera-
ture on water and wastewater disinfection with
ozone indicated that the following statements are
valid:
1. Ozone is a powerful bactéricide in water or
wastewater.
2. Ozone is a powerful virucide in water or
wastewater.
3. Most waters and wastewaters will have a
higher ozone requirement on a mg/liter basis than
the chlorine requirement to accomplish the same
disinfection.
4. Cost of disinfection with ozone is greater
than the cost of disinfection with chlorine.
5. Ozone is not presently widely used in the
U.S. for either water or wastewater disinfection. It
is widely used to disinfect bottled water in the
U.S.
6. Ozone will probably never be widely used
in this country for municipal water disinfection,
because of the requirement in most states for the
presence of residual disinfectant in the water after
some specified contact time.
7. Ozone will probably never be widely used
in this country for municipal wastewater disinfec-
tion so long as cost is a major design consideration.
8. Ozone disinfection will probably be a unit
process in most wastewater reclamation plants for
potable reuse applications.
9. Ozone is toxic to man and should not be
inhaled.
10. Additional research on ozone disinfection
should focus on the following areas:
a. Disinfection efficiency against other or-
ganisms than those studied to date.
b. New contacting schemes to increase mass
transfer and reduce capital costs of contactors.
c. Ozone production and related equipment.
d. Ozone measurement and monitoring
systems in water.
e. Toxicity of ozonation products in disin-
fected water or wastewater.
f. BODs, TOC, and COD relationships in
ozone disinfection.
g. Ozone reaction products in the disin-
fected water or wastewater.
h. Physiological effects of low ozone con-
centrations on man.
January 1975 151
 The question has been asked, "Can ozone ever
replace chlorine?" 16 The answer to this question
is a flat no, if complete replacement is what the
question really asks. If the question means, are
there disinfection situations where ozone could be
competitive with chlorine, then the answer is yes.
Presently these locations where ozone is competi-
tive with chlorine are few in number, but changes
in local regulatory requirements, availability of
chlorine, toxicity of chlorine compounds, and new
research information could change the existing
situation to a situation more favorable for applica-
tion of ozone in water and wastewater disinfec-
tion.

ARTICLES REVIEWED
Bailey, P., Reactions of ozone with organic compounds, amines, phosphines, arsines, and sulfides, Chem. Rev., 58, 2,977,
1958.
BaileyyP., Ozone reactions with organic compounds, Adv. Chem. Ser. 112, American Chemical Society Publishers, 1972, 9.
Binovi, R. D., Toxicity of chlorinated, dechlorinated, ozonated effluents to fathead minnow larvae (pimephales promelas),
Unpublished master's thesis, University of Cincinnati, Cincinnati, Ohio, 1974.
Davis, E.M.,Whitehead,L.W., and Moore, J. D., Disinfection,/. WaterPollut. Cortt. Fed., 46,6,1181, June 1974. '
Diery, R-, et al. Effect of pH on the stochiometric determination of ozone, Anal. Chem., 45, 2,402,1973.
Downloaded by [Cornell University Library] at 18:25 19 November 2014

Eisenhaut, H., Ozonation of phenolic wastes,/. WaterPollut. Cont. Fed., 40,1887,1968.

Eisenhaur, H., Increased rate and efficiency of phenolic waste ozonation, /. Water Pollut. Cont. Fed., 43,2,201,1971.
Hann, V. A. and Manley, T. C, Ozone, Encyclopedia of Chemical Technology, 9,735, 1952.
Mix, T. W. and Scharen, H., Organic solute detection, Am. Soc. Mech. Eng., Aerospace Division, Intersociety Conference
on Environmental Systems, Seattle, Washington, July 1974.
Walter, R. H. and Sherman, R- M., Ozonation of lactic acid fermentation effluent,/. WaterPollut. Cont. Fed., 46,7,1800,
July 1974.
REFERENCES
1. Kinman, R. N., Ozone in water disinfection, in Ozone in Water and Wastewater Treatment, Ann Arbor Science
Publishers, Ann Arbor, Michigan, 1972, chap VII.
2. Sonozone waste Water treatment systems brochure, Telecommunications Industries, Lindenhurst, New York, 1974.
3. Broadwater, W. T., Hoehn, R. C, and King, P. H., Sensitivity of three selected bacterial species to ozone, J. Appl.
Microbiol, 26, 391, 1973.
4. Katzenelson, E., Kletter, B., Schechter, H., and Shuval, H. I., Inactivation of micro-organism by ozone, ACS Annual
Meeting, Dallas, Texas, April 1973.
5. Majumdar, S. B., Ceckler, W. H., and Sprout, O. J., Inactivation of poliovirus in water by ozonation, J. Water Pollut.
Cont. Fed., 45(12), 2433, December 1973.
6. Ingols, R. S., Fetner, R. H., and Eberhardt, W. H., Determining ozone in solution, Adv. Chem. Ser. 21, Ozone
Chemistry and Technology, 102, March 1959.
7. Ingols, R. S. and Fetner, R. H., Bactericidal activity of ozone and chlorine against escherichia coli at 1°C, Adv.
Chem. Ser. 21, Ozone Chemistry and Technology, 370, March 1959.
8. Nebel, C., Gottschling, R. D., Hutchinson, R. L., McBride, T. J., Taylor, D. M., Pavoni, J. L., Tittlebaum, M. E.,
Spencer, H. E., and Fleischman, M., Ozone disinfection of industrial-municipal secondary effluents, J. Water Pollut.
Cont. Fed., 45(12), 2493, December 1973.
9. Nebel, C., Unangst, P. C., Gottschling, R. D., Hutchinson, R. L., McBride, T. J., and Taylor, D. M., Ozone
disinfection of combined industrial and municipal secondary effluents - part II - pilot plant studies, Proc. Purdue
Ind. Waste Conf., Part 2, 1056, May 1972.
10. Zenz, D. R. and Weingarden, M. J., Ozonation of microstrained secondary effluent, Symp. Ozonation in Sewage
Treatment, University of Wisconsin, Milwaukee, Wisconsin, November 1971.
11. Kinman, R. N., Ozone disinfection of wastewaters at low temperatures, Proc. Symp. Wastewater Treatment in Cold
Climates, University of Saskatchewan, Saskatoon, Saskatchewan, Canada, March 1974, 507.
12. Rosen, H. M., Use of ozone and oxygen in advanced wastewater treatment,/. Water Pollut. Cont. Fed., 45(2), 2521,
December 1973.
13. Nebel, C., Unangst, P. C, and Gottschling, R. D., An evaluation of various mixing devices for dispersing ozone in
water, Waterand Sewage Works, Ref. Number, p. R-6, April 1973.
14. Kinman, R. N., Analysis of ozone-fundamental principles, Proc. First Int. Symp., Ozone 101, Washington, D.C.,
December 1973.
15. Hazucha, M., Silverman, F., Pavert, C., Field, S., and Bates, D. V., Pulmonary function in man after short-term
exposure to ozone, Arch. Environ. Health, 27, 183, 1973.
16. McBride, T. J. and Taylor, D. M., Can ozone ever replace chlorine, Water Wastes Eng., 10, 5, 29, 1973.
17. Manual of Water Supply Practice, Water Chlorination Principles and Practices, Am. Water Works Assoc, M-20, 2,
1973.

152 CRC Critical Reviews in Environmental Control