Chemosphere No. i, pp 9 - 28, 1978. Pergamon Press. Printed in Great Britain.

CHLORINATION AND OZONATION

IN

WATER AND WASTEWATER TREATMENT

John D. Keenanand David A. Hegemann

Department of Civil and Urban Engineering, I13 Towne Building

University of Pennsylvania, Philadelphia, Pa. 19104

(~eceived in The Netherlands 26 October 1977; receivecl in UK for publication 28 November 1978)
Nearly a century has passed since chlorine and ozone were f i r s t tested as disinfecting a-

gents for potable water. The concern for the public health aspects of water quality has resulted

in the widespread adoption of disinfection, with chlorination and ozonation being the most com-

mon methods. The success of disinfection in developed areas is underscored by the virtual e l i -

mination of waterborne diseases caused by enteropathogenic bacteria and viruses. Disinfection,

the reduction of pathogen numbers to a level having no significant health threat, can be accom-

plished by several means including physical treatment, i r r a d i a t i o n , and the addition of chemicals

such as metal ions, alkalis and acids, surface active agents, and oxidants, l Naturally, not

a l l of these have seen equal use in the past, and i t appears certain that p r i o r i t i e s as well as

physical r e a l i t i e s w i l l result in changes in the future. Currently, chlorination is the over-

whelming choice as a disinfectant for water and wastewater. However,chlorine is not a perfect

disinfectant and the magnitude of its shortcomings are being reassessed. Ozone, the next favored

choice, has received renewed promotion in l i g h t of the above, while other disinfectants show one

or more serious limitations making them unsuitable for widespread use in municipal treat-

ment. In recognition, this review is limited to a comparison of chlorine and ozone. The prac-

tice of disinfection is influenced by a number of factors. In this paper, these are divided in-

to two categories, chemical and biological. The relevance of these factors is then noted for

the treatment of potable waters and of wastewaters.

i0 No. i

CHEMISTRY OF DISINFECTION

Chlorine Reactions in Aqueous Solution.

In the absence of competing reactions, c h l o r i n e added to water r a p i d l y ( a f t e r a few seconds)

forms a mixture of hypochlorous and h y d r o c h l o r i c acids in the f o l l o w i n g manner:

C12 + H20 ~ HOCI + H+ + CI- (I)

In d i l u t e s o l u t i o n s w i t h pH l e v e l s above 4, the reaction proceeds nearly to completion. HOCI, a

weak acid, d i s s o c i a t e s almost instantaneously i n t o hydrogen and h y p o c h l o r i t e ions:

HOCI • H+ + OCI- (2)

This r e a c t i o n has a K =2.95 x 10 -8 in aqueous s o l u t i o n . Chlorine e x i s t i n g as h y p o c h l o r i t e ions
a
and aqueous Cl 2 is free a v a i l a b l e c h l o r i n e .
The h y p o c h l o r i t e sources, calcium h y p o c h l o r i t e and sodium h y p o c h l o r i t e , i o n i z e :

Ca(OCI)2 + H20 w~-~Ca ++ + 20CI- + H20 (3)

Na(OCI) + H20 ~ Na+ + OCI- + H20 (4)

and the h y p o c h l o r i t e ions e s t a b l i s h the e q u i l i b r i u m indicated in Eqn (2). Free a v a i l a b l e chlo-

rine residual is l o s t over time as a r e s u l t of v o l a t i l i z a t i o n of C12 and/or various decomposition

reactions i n c l u d i n g those catalyzed by u l t r a v i o l e t light. 3

Breakpoint Reactions.
The reactions between c h l o r i n e and reduced compounds are of great s i g n i f i c a n c e . The reac-

tions involved in the breakpoint phenomenon are characterized below and are summarized in Fig-

ure I. When c h l o r i n e is added to water containing ammonia n i t r o g e n , chloramines are produced:

NH3 + HOCI • , NH2C1 + H20 (5)

NH2CI + HOCl • ] NHCl2 + H20 (6)

,NHCI2 + HOCI • • NCI3 + H20 (7)

Chlorine e x i s t i n g in combination w i t h ammonia (or organic nitrogen) compounds is combined a v a i l a -

ble c h l o r i n e . The extent of these reactions depends h e a v i l y upon CI2:NH 3 r a t i o s , pH, i n t e r f e r i n g

i m p u r i t i e s , and temperature. At neutral pH the product is almost e n t i r e l y monochloramine, which

forms w i t h i n minutes.
Further a d d i t i o n of c h l o r i n e r e s u l t s not only in reactions (6) and (7)
1
but also competing reactions (unbalanced) which remove nitrogen from the system:

NH3 + C12 ~ N2~ + HCI (8)

NH2CI + ci 2 + ,2o?+ HCl (g)

NHCI 2 + H20 ~ N20~+ HCI (I0)
No. I II

Mole Ratio CI2:NH4 - N

0.5 l 1.5 2
lO

7
cp
6

.+ofY
L
o
5

2 // i-'J
,~Breakpoint, e
l Combined P r e d o m i n a t e s Predominates

l 2 3 4 5 6 7 8 9 lO II 12
Chlorine Dosage
mg/l

Figure l Typical Breakpoint Chlorination Curve.4

Nitrogen, and to a lesser extent nitrous oxide and nitrogen t r i c h l o r i d e , are the principal gase-

ous products of the breakpoint reactions. 4 The "dip" in Figure l represents the loss of chlorine

residual due to concomitant oxidation of nitrogen and reduction of chlorine. To the l e f t of the

breakpoint, combined chlorine residuals dominate, whereas free chlorine residuals dominate to the

right.

Reaction with Selected Inorganics.

Chlorine reacts with other inorganic reducing agents. Generally the result is to reduce

measured chlorine residual. The reactions presented below are stoichiometric simplifications of

actual reactions and are subject to numerous interferences. White discussed many of these in

further detail. 3 Chlorine reacts rapidly with inorganic carbon in the following manner:

C + 2CI 2 + 2H20 ) 4HCI + C02f (]l)

In alkaline solutions (pH 8.5 or higher) chlorine reacts with cyanide to form cyanate:

2CI 2 + 4OH- + 2NaCN ) 2NaCNO + 4Cl" + 2H20 (12)

or with higher concentrations, to form nitrogen gas:

12 No. i

5CI 2 + I0 OH- + 2NaCN ~ 2NaHCO3 + I0 CI- + N~+ 4H20 (13)

Reaction with dissolved methane does not occur in natural systems although the reaction is explo-

sive at elevated temperatures:

CH4 +4Cl2 ) CCl4 + 4HCl (14)

Reaction with dissolved hydrogen sulfide forms either free sulfur precipitate or dilute sulfuric

acid, depending on pH and chlorine concentration:

H2S + Cl 2 ) S~+ 2HCI (15)

H2S + 4CI 2 + 4H20 ) H2SO4 + 8HCI (16)

S u l f u r d i o x i d e , added to water forms sulfurous acid which is o x i d i z e d to s u l f u r i c acid:

H2SO3 + HOCI ) H2SO4 + HCI (17)

Ferrous i r o n , such as the commonly occurring ferrous bicarbonate is o x i d i z e d to f e r r i c hydroxide

in an almost instantaneous r e a c t i o n :

2Fe(HC03) 2 + C12 + Ca(HC03) 2 ) 2Fe(OH) 3 + CaCI2 + 6C02 (18)

Reduced manganese species are o x i d i z e d slowly and o n l y by f r e e a v a i l a b l e c h l o r i n e in a l k a l i n e so-

l u t i o n s to manqanese d i o x i d e , which p r e c i p i t a t e s :

MnSO4 + C12 + 4NaOH > MnO2 + 2NaCI + Na2SO4 + 2H20 (19)

Reactions w i t h Organics.

Chlorine reacts w i t h organic contaminants to form chloroorganic end products. The occur-

rence of such reactions is an area r e q u i r i n g much f u r t h e r research, and the problem is enormous-
5
l y complex, due to the great number of organics and t h e i r low concentrations. Murphy et a l .

ran extensive tests on pure compounds known to be susceptible to c h l o r i n a t i o n , using conditions

s i m i l a r to normal operating procedures. They concluded t h a t only organics w i t h ring structures

and e l e c t r o n a c t i v a t i n g substituents ( e . g . , -OH groups), or amino groupings can be c h l o r i n a t e d .

Rates were g e n e r a l l y found to be much lower than t y p i c a l i n o r g a n i c r e a c t i o n s .

Morris 6 concluded t h a t there are f o u r p r i n c i p a l types of reactions of h y p o c h l o r i t e with or-

ganic matter that need to be considered: addition to o l e f i n i c bonds

HH
i I
RCH=CHR + HOCI ) R-C-C-R (20)
Is
OH Cl
No. 1 13

activated ionic substitution, such as

C6H50H + HOCl ~ C6H4CI OH + H20 (21)

0 0
Jt i/
CH3C-CH3 + HOCI ) CH2CI-C-CH3 + H20 (22)

oxidation, with reduction of hypochlorite to chloride

R-CHO + Hr)Cl • RCOOH+ H+ + Cl- (23)

and substitution of chlorine for hydrogen on a nitrogen atom

H Cl
I I
R-N-R + HOCI ) R-N-R + H20 (24)

Simple a l i p h a t i c s u b s t i t u t i o n is not expected. The f i r s t three of these represent a d d i t i o n a l

chlorine demand, as the chlorine atom no longer is capable of acting as an o x i d i z i n g agent.

The current e d i t i o n of Standard Methods7 discusses the various methods f o r determination

o f free and combined chlorine residuals, and l i s t s seven accepted and one t e n t a t i v e procedure.

Routine and rapid analysis of chlorine concentrations is generally quite e a s i l y accomplished.

Ozone Reaction i n Aqueous Solution.

Ozone is more soluble than oxygen in water, but the much lower a v a i l a b l e p a r t i a l pressure

makes i t d i f f i c u l t to obtain more than a few ppm under normal conditions of temperature and

pressure. Ozone is unstable, decomposing to oxygen in minutes in aqueous media. Neutral salts

and hydroxyl ions accelerate this decomposition which in pure aqueous solution occurs as:

03 + H20 ) H03+ + OH- (25)

H03+ + OH- ) 2H20 (26)

03 + HO2 ) HO + 202 (27)

HO + HO2 ) H20 + 02 (28)

The free radicals HO2 and HO r e t a i n great o x i d i z i n g pot ent ial and they are reactive with many

common impurities such as metal salts and organic matter. Efforts to determine precise rates

of ozone decomposition have been hampered due to the i n a b i l i t y to remove or control the con-

centration of such i m p u r i t i e s , r e s u l t i n g in poor experimental r e p r o d u c i b i l i t y . 9

Reaction with Inorganics.

Ozone reacts with many inorganic reduced species in re-dox reactions. Those l i s t e d here

are stoichiometric s i m p l i f i c a t i o n s , and furthermore, many are subject to interferences under

 14 No. 1

varying conditions. Ozone reacts with ammonia rather slowly according to the formula:

2NH3 + 302 ) 2NO3 + 3H20 (29)

Only under alkaline conditions does this reaction occur to any significant degree, as carbona-

ceous materials are oxidized preferably and ozone decomposes before ammonia is reacted. Ozone

addition results in the oxidation of reduced iron and manganese to insoluble oxides at a rapid
rate: 7

Fe2+ + 03 + H20 ) Fe(OH)3 + 02 + H20 (30)

Mn2+ + 03 + H20 ) MnO2 + 02 + H20 (31)

Reaction with reduced sulfur is strongly dependent upon pH, with low values favoring greater

oxidation. End products are either elemental sulfur or sulfate: lO

S= + 03 + H20 ~ S + 2OH- + 02 (32)

S: + 403 > S04: + 402 (33)

The reaction of ozone with cyanide is rapid, e s p e c i a l l y in the presence of s u l f a t e salts of se-

lected metals. The general reaction is of the form I I

CN- + 03 + H20 ,~ CNO- + H20 (34)

Reaction with Organics.

Ozone reacts r a p i d l y with various organics and u s u a l l y to a greater extent than chlorine.

Ozone r e a d i l y attacks carbon-carbon double bonds, certain carbon-nitrogen double bonds, and nu-

cleophiles such as amines and s e l i n i d e s . Other bonds, such as carbon-hydrogen react favorably

but only in the absence of competition from the above. 12

Ozone attack of double bonds proceeds as f o l l o w s , depending upon the nature of the R

groups.

0-0-0
! \
R2C=CR2 + 03 ) R2C CR2 0-0

~-O-
O-OH
R2C /CR2 / (etc)
(35)
 No. I 15

The ozonide and peroxide intermediates are unstable and decompose by hydrolysis with water

to carbonyl products, especially in the presence of zinc. For example13

03
CH3 CH=CHCH3 Zn, H20 ) 2CH3C~'H (36)

A competing reaction to ozonolysis when certain hindered olefins are involved is the partial

cleavage of the double bond to form epoxides. However, epoxides, many of which are suspected

mutagens, have not been detected after ozonation of waters containing t h e i r precursors. 14

Much has been written about the i n a b i l i t y to adequately measure ozone residuals in wa-
ter.7, 15, 16 Because of ozone's i n s t a b i l i t y in water, most analytical methods involve low pH

solutions at temperatures near O°C. The current edition of Standard Methods l i s t s three approved

methods, 7 of which only the iodometric method is considered quantitative.

DISINFECTING ACTION

Waterborne diseases which are s i g n i f i c a n t health hazards have been considered elsewhere. 3

These diseases are transmitted by water, but not necessarily by water alone, as food and personal

contact are often important factors. The more important include typhoid fever, cholera, amebic

dysentery, gastroenteritis and infectious hepatitis.

Chlorination.

The effectiveness of chlorine as a disinfection agent is largely dependent on i t s form.

Hypochlorous acid is recognized as the most effective chlorine residual. This is due to its

ease of penetration of cell walls, attributed to i t s low molecular weight and electrical neu-

trality. The hypochlorite ion has been estimated to be 80 to 300 times less e f f i c i e n t than

HOCI depending on such conditions as temperature and organism studied. 3 The ratio of acid to

ion is a function of pH: chlorination efficiency is drastically impaired at pH values exceed-

ing 9.0. Chloramines appear even less potent than hypochlorite ion under similar circumstances.

Nuisance residuals, such as N-chloro-organics show l i t t l e i f any disinfecting capability. The

effectiveness of disinfection also depends upon organism type, contact time, temperature, and

the nature of the residual. Varma and Baumann17 reviewed the chlorine residuals and contact

times needed to k i l l vegetative bacteria, spores, viruses and amebic cysts. They plotted time

versus free available chlorine residual as straight lines on log-log paper. Note that a com-

parison between chlorine dose and percent k i l l would be less meaningful due to the i n a b i l i t y to

keep chlorine species d i s t r i b u t i o n constant. Total and combined residual concentrations are al-
so less satisfactory as parameters because water quality would not remain constant.
16 No.1

Ozonation.

Quantitative studies of ozone as a disinfectant are d i f f i c u l t because of the i n s t a b i l i t y

of ozone solutions. However, i t is agreed that ozone is effective at much lower concentrations

than chlorine, that disinfection occurs quite rapidly once a c r i t i c a l residual level is reached,

but that very l i t t l e action is observed below this concentration. This has lead various re-

searchers to conclude that ozonation is limited by ozone-organism contact which in turn is l i m i -

ted by ozone demand. Rosen et al. 18 have successfully applied the assumption of bacterial lysis

in modelling ozone action, and point to the fact that i t f i t s observed disinfection kinetics.

Ozone inactivation appears to be unspecific~ occurring in much the same manner as described for

organic molecules.

Venosa19 has recently compiled a review of the use of ozone as a disinfectant, and he con-

cluded that much controversy and confusion are apparent in published accounts. However, Kinman20

pointed out the general agreement that r e l a t i v e l y low concentrations of 03 (less than O.5ppm)

w i l l achieve disinfection i f not s t e r i l i z a t i o n . Farook et al. noted that acidic pH values pro-

vided better disinfection than alkaline conditions because of greater ozone s t a b i l i t y , and thus

higher ozone residuals. No pH effect is apparent when a constant ozone residual is maintained.21

Kinman20 reported 03 concentrations as low as O.Ol ppm as toxic to Escherichia coli and

Streptococcus faecalis at pH 7.0 and 25° C in pure systems. Figure 2 shows his results comparing

disinfectants of pure E. coli (lO 6 organism/liter) cultures. Katzenelson's 22, 23 experimenta-

tion with ozone yielded two stage shaped inactivation curves for E. c o l i , with a rapid f i r s t

stage followed by a much slower second one. He noted that clumping would account for these phe-

nomena, and found that steps to reduce clumping lead to longer f i r s t stage periods. He22 found

similar curves for inactivation of poliovirus l and coliphage TO, noting that f i r s t stage inac-

t i v a t i o n was more rapid than for that of E. c o l i . Majumderet ai.24 experimented with polio-

virus in batch studies using d i s t i l l e d water and primary and secondary wastewater. They ex-

pressed the rate of poliovirus inactivation as empirical exponential relationships.

POTABLE WATER PRODUCTION

Chlorination Applications.

Chlorination was f i r s t practiced as a means of disinfection, which remains i t s principal

use today. However, other applications of chlorine have also proved beneficial and a few of

the more i m p e r t a n t a p p l i c a t i o n s are discussed below. Since the fOnTL and c o n c e n t r a t i o n o f the
No. 1 17

6
0 0
0.45 ppm Monochloramine
5

4 0.55 ppm Iodine

u~ ~ 0 . 5 6 ppm Free Chlorine

c

3 O.Ol ppm Ozone

0

..J

1 t "5 I i I I I I t
0 l 2 3 4 5 6 7 8 9
Time, minutes
Figure 2 Destruction of E. Coli by Disinfectants in Water20

chlorine residual, and not the amount of chlorine added, influence disinfection capability, most

systems use the former as a feedback for determining the l a t t e r . As a guideline, the United

States Public Health Service has proposed recommendedminimum safe residuals. These are: depen-

ding upon pH, at least l.O ppm chloramine residual after 60 min., or 0.2 to 0.8 ppm free residual

after lO min. The longer time a l l o t t e d before measuring chloramine resiudals reflects the fact

that with combined available chlorine the longer persistence allows longer contact periods to

p a r t i a l l y offset its reduced potency with respect to the free available form.

Most treatment operations are currently geared to meet governmental standards, which are

usually in terms of coliform bacteria. There is considerable debate as to the effectiveness of

the standards in insuring pathogen free water especially since chlorination is much more ef-

fective against the coliforms than against certain cyst forming bacteria and many viruses. 25

However, except in extreme cases, observations have upheld the comparatively diminutive ranks of

pathogens when coliform levels are low.

The presence of tastes and odors, while objectionabie in their own right, are to be fur-

ther avoided because of popular opinion that such waters are unsafe. Taste and odors are often
26, 27
due to a combination of causes including both chemical and microbial factors. Chlorina-
 18 No. 1

t i o n is e f f e c t i v e in d e s t r o y i n g both a l g a l species and actinomycetes, but heavy d e p o s i t s o f pre-

vious growth must be removed to e l i m i n a t e problems associated w i t h t h e i r decomposition. Chlori-

n a t i o n using f r e e r e s i d u a l s can o f t e n o x i d i z e o f f e n d i n g organics to non-odorous species. How-

ever, c e r t a i n c h l o r i n a t e d compounds, such as phenols, can i n t e n s i f y t a s t e and odor problemsw

C h l o r i n a t i o n can be s u c c e s s f u l l y employed in the removal o f iron and manganese. These ca-

t i o n s are much more s o l u b l e in the reduced form. O x i d a t i o n by c h l o r i n e leads to the f o r m a t i o n o f

relatively i n s o l u b l e compounds w i t h a v a i l a b l e anions, causing p r e c i p i t a t i o n . 3

Maintenance of a proper c h l o r i n e r e s i d u a l in the f i n a l product w i l l a f f o r d p r o t e c t i o n in

the d i s t r i b u t i o n system a g a i n s t contamination by pathogens and b i o f o u l i n g by chemoautotrophic

bacteria. Because o f t h e i r longer p e r s i s t e n c e in w a t e r , combined c h l o r i n e r e s i d u a l s are most

o f t e n used f o r t h i s purpose. However, severe problems r e q u i r e l a r g e doses o f free c h l o r i n e ,

w i t h the l i k e l i h o o d of t a s t e s and odors due to d i c h l o r a m i n e and/or n i t r o g e n t r i c h l o r i d e , 3

C h l o r i n a t i o n Problems.

Although modern c h l o r i n a t i o n p r a c t i c e has been very successful as a p p l i e d to p o t a b l e w a t e r ,

c e r t a i n problems s t i l l require attention. C h l o r i n e in s u f f i c i e n t c o n c e n t r a t i o n causes r e s p i r a t o -

ry impairment w i t h extreme d i s c o m f o r t . Proper o b s e r v a t i o n o f recommended precautions in t r a n s -

D o r t a t i o n and handling have been shown to provide acceptable margins of s a f e t y .

There is no d i r e c t evidence o f adverse p h y s i o l o g i c a l e f f e c t s caused by long or s h o r t term

I n g e s t i o n o f c h l o r i n a t e d water. There are numerous cases o f short term i n g e s t i o n of abnormally

high free c h l o r i n e r e s i d u a l s (50-90 ppm) durina emergency t r e a t m e n t s i t u a t i o n s w i t h no e f f e c t

upon the o o p u l a t i o n . Studies w i t h mice showed t h e i r a b i l i t y to t o l e r a t e 200 ppm and m a i n t a i n

normal growth. Seven generations of r a t s survived I00 ppm w i t h o u t p h y s i o l o g i c a l damage or

shortened l i f e s p a n . Since n e a r l y a l l consumers r e c e i v e water w i t h l i t t l e or no r e s i d u a l remain-

3
ing, danger from t r a d i t i o n a l l y identified c h l o r i n e species is viewed as nonexistent_

The e f f e c t s o f c e r t a i n organic chemicals r e c e n t l y found in municipa| water s u p p l i e s are

now of concern. The l i s t s o f organics i d e n t i f i e d are l e n g t h y , but are estimated to contain at

most about one q u a r t e r o f the probable t o t a l . 2 8 I n t e r e s t has been s p e c i f i c a l l y expressed in the

presence o f c h l o r i n a t e d species, and the e x t e n t to which c h l o r i n a t i o n accounts f o r t h e i r produc-

tion. 5, 6, 29-34 B e l l a r et a i . 3 0 measured the d i s t r i b u t i o n of halofornl species in c h l o r i n a t e d

surface water in Ohio. T h e i r r e s u l t s c o r r e l a t e d well w i t h the f i n d i n g s of Rook 31 in Holland.

Chloroform (CHCI 3) predominated w i t h amounts o f CHCI2Br, and CHBr2 always d e t e c t e d . 29 Both r e -

No. 1 19

searchers f a i l e d (using simple techniques) to discover further reaction products with organics

and free chlorine residual.6 Steney34 concluded that the trihalomethane precursor is a mixture

of humic substances and simple low molecular weight compounds containing the acetyl moiety. Re-

action with ammonia effectively avoids trihalomethane production. Althoughchloroform is a

known animal carcinogen, 35 and the other haloforms are suspect, adverse human health effects of

ingesting these concentration levels have not been demonstrated. Gaffney33 recently concluded

that chlorination can produce polychlorinated biphenyls (PCB's) from biphenyl precursors in the

absence of interfering reactions. Such PCB's are highly toxic to a number of ecosystem compo-

nents.

The issue of chlorinated organics formed during water treatment has become a p r i o r i t y topic

for the U. S. Environmental Protection Agency.29 Morris,6 among others, has called for inten-

sive investigation to determine the extent of chlorine addition to other organic species. The

need is also present to study human health effects, as well as treatment operation to determine

methods for precursor removal and methods to prevent their chlorination.

Ozonation Applications.

The use of ozone for potable water treatment has been known since the beginning of the cen-

tury, and ozonation f a c i l i t i e s are in use at Nice, Chartres, Paris, etc. 36 Ozoneis used primari.

ly as a disinfectant and also for the removal of tastes, odors and certain cations. Ozonation

achieves rapid and complete disinfection and is usually applied after flocculation, settling

and f i l t r a t i o n , and is followed, as needed, for distribution system protection, by a post chlo-

rination step. The ozone dosage required for successful potable water treatment varies from

0.2 to 1.5 ppm, depending on raw water quality. 37 Ozonedemandmust be satisfied before f u l l

disinfection can be achieved. In practice, an ozone residual is established which is measured

5 minutes after injection. T h i s residual is maintained at O.l to 0.2 ppm for the destruction of

bacteria and 0.4 ppm for the destruction of viruses. 38 The actual residual varies with each

i n s t a l l a t i o n due to interfering effects on available analytical procedures.

Ozone is known to deal e f f e c t i v e l y with many taste and odor sources. This is in contrast

to chlorine, which, unless carefully applied, can introduce additional disagreeable products.

Diaper38 reports that ozone doses of l to 2 ppm w i l l eliminate chlorophenol induced tastes and

destroy bhenol at concentrations up to 0.2 ppm. In addition to oxidation, ozonation achieves

removal through the aeration due to the large gas volumes carrying the ozone.
 20 No. I

Ozone can remove iron and manganese by oxidation to insoluble forms. Approximately

1.5 ppm was required for removal at the Dusseldorf Water Works in Hestern Germany. Ozoneem-

ployed for this purpose is added prior to coagulation. 39 Problems with a i r bubble accumulation

on oxidized p a r t i c l e s , leading to f l o t a t i o n and subsequent scum formation were reported at

39
Philadelphia. However, water sprays were effective in stopping such surface accumulation.

Ozonation is effective in oxidizing many organics. The yellow-brown humus color is oxi-

dized, producing a clear product. Reduction in t u r b i d i t y has also been noted.38 Love et ai.32

investigated preozonation as a step to reduce haloform formation. Results showed that although

ozone alone would not form trihalomethanes, moderate levels of ozonation, followed by chlorina-

tion produced as much (or more) chloroform as chlorination alone.

Ozonation Problems.

Although excessive costs have inhibited i t s use in the past, recent improvements in ozone

technology promise to reduce this price d i f f e r e n t i a l . The Micellization/Demicellizationprocess

and the microzon process (an abridgement of the former) use ozone's effective action on organic
40
colloids to economize on other treatment steps. Improvementshave also been noted in generator

construction and application techniques. The l a t t e r includes better mixing basins and recycling

of spent gas to the ozone generator or to water upstream as a pre-ozonation step.

The lack of an ozone residual is a problem, although practioners in France have downplayed

i t s importance in providing system protection. They note the elimination of waterborne disease,
41, 42
and add that residual maintenance offers l i t t l e protection against gross contamination.

However, maintaining a chlorine residual is valuable, as a protective measure, as an aid in e l i -

minating biofouling of pipes, and furthermore, many states require residual maintenance. Addi-

tion of a postchlorination step to provide a residual would increase the cost of ozone treatment,

further lessening the opportunity for i t s adoption.

WASTEWATER TREAT[]ENT

Chlorination Applications.

The practice of wastewater disinfection, i t s e l f of rather recent o r i g i n , is p r i n c i p a l l y a

United States development. Chlorination was given primary consideration, in this application,

and subsequently, i t has been found to reduce odors and BOD, and to p a r t i a l l y destroy certain

toxic materials. Chlorination efficiency in wastewater disinfection is dependent on the nature

of the waste and the degree of treatment. Many wastewater constituents react with chlorine
No. 1 21

to reduce the available residual. Waste pH also effects the nature of the reactions and subse-

quent disinfecting capability. Effluents with low ammonia nitrogen concentration (I-2 ppm)

may be treated economically to free chlorine residual stages, with further nitrogen reduction

occurring at the breakpoint. I,lastes containing high nitrogen levels can be treated economically

only to the monochloraminestage, resulting in longer contact times for equal disinfection.

Current practice tends to indicate that only a very few wastewater treatment 'plants achieve sa-

tisfactory disinfection, as determined by compliance with coliform standards. 3

Odors in wastewater are usually the result of putrefaction of proteins to odoriferous de-

rivatives of amino acids and hydrogen sulfide. Chlorine acts to oxidize the odorous compounds

and to i n h i b i t bacterial growth. Howeverthe amount of chlorine necessary to achieve these

goals is often large and d i f f i c u l t to accurately determine. 3

Chlorine reduces BOD, partly by oxidizing organic matter and partly by substitution and

addition to unsaturated and saturated compounds, resulting in products inert or resistant to bac-

t e r i a l action. Chlorination is also effective in the removal of grease, the destruction of cya-

nide wastes, the removal of reduced metallic ions and the decomposition of organics such as phe-
3
nol.

Chlorination Problems.

Chlorination of wastewater has been under increasing attack as causing damage in receiving

waters and as a source of harmful chlorinated byproducts. A number of studies have shown waste-

water chlorination to have an adverse effect on aquatic organisms, although i t is not clear what

constitutes a harmful, or lethal dose. Brungs42 noted in his review that while chlorination is

often blamed, some degree of degradation of the aquatic environment near waste treatment dis-

charge sites is a common observance, whether the effluent was chlorinated or not. Chlorine re-

sidual effects are marked, with persistence for periods longer than a few hours as previously

believed.

Ward et ai.43 disinfected activated sludge effluent in a two staged experiment. The le-

vels of disinfectant necessary to achieve coliform standards were tested for l i f e cycle effects

on fathead minnows (Pimephales promelas). Chlorination proved to be the most toxic, but dechlo-

rination with sulfur dioxide eliminated the problem. Esvelt et ai.,44 in studies at eight San

Francisco Bay area locations, also noted that the t o x i c i t y was reduced by dechlorination.

Gehrs45 noted that the percentage of successful carp egg hatching was severely reduced long be-
22 I;o. 1

f o r e t o x i c e f f e c t s were noted. Toetz 46 studied the e f f e c t o f combined and f r e e r e s i d u a l s on

phytoplankton uptake o f i n o r g a n i c n i t r o g e n , f i n d i n g t h a t i n i t i a l c o n c e n t r a t i o n s as low as

0.023 ppm depressed n i t r a t e uptake by 50 percent. He observed t h a t uptake o f n i t r a t e and am-

monia, w h i l e f o l l o w i n g Michaelis-Menton k i n e t i c s in c o n t r o l s , f a i l e d to do so in the presence of

0.I ppm of e i t h e r c h l o r i n e r e s i d u a l . This may have adverse e f f e c t s on ecosystem p r o d u c t i v i t y .

The e f f e c t o f d i l u t i o n in m o d i f y i n g adverse e f f e c t s has received much mention but l i t t l e direct

study. Z i l l i c h 47 p o i n t s out t h a t f i s h have been observed to avoid areas c o n t a i n i n g t o x i c con-

c e n t r a t i o n l e v e l s o f many substances, i n c l u d i n g c h l o r i n e .

Speculation about the production o f harmful c h l o r i n a t e d organics in wastewater t r e a t m e n t

i s s i m i l a r to t h a t voiced f o r p o t a b l e water. The magnitude o f the problem is increased by the

much l a r g e r range and c o n c e n t r a t i o n l e v e l s of organics present in e f f l u e n t s . Gaffney 33 showed

t h a t c h l o r o b i p h e n y l s could be formed by c h l o r i n a t i n g e f f l u e n t s c o n t a i n i n g biphenyl p r e c u r s o r s .

Haloform production can also occur. The e f f e c t o f d e c h l o r i n a t i o n on c h l o r i n a t e d o r g a n i c produc-

t i o n is unknown but would be v a l u a b l e i n f o r m a t i o n since i t is beneficial in reducing r e s i d u a l

toxicity.

Ozonation A p p l i c a t i o n s .

C u r r e n t l y , ozonation is not used in f u l l scale wastewater t r e a t m e n t . However, r e c e n t l a -

boratory pilot p l a n t s t u d i e s have i n d i c a t e d t h a t ozone can be c o m p e t i t i v e w i t h c h l o r i n a t i o n - d e -

c h l o r i n a t i o n on the basis of c o s t , w h i l e e l i m i n a t i n g the problems associated w i t h c h l o r i n e side

reactions.

Studies by Nebel e t a l . 48 i n d i c a t e d t h a t d e s t r u c t i o n of microorganisms by ozone takes

place s i m u l t a n e o u s l y w i t h the o x i d a t i o n o f p o l l u t a n t s . Therefore, the amount of ozone r e q u i r e d

to produce a given l e v e l o f d i s i n f e c t i o n is dependent on the nature of the e f f l u e n t . In g e n e r a l ,

ozone dosages o f 5 to I0 ppm are adequate to achieve d i s i n f e c t i o n to a p l a t e count of 200/100 ml

o f fecal c o l i f o r m a t y p i c a l wastewater requirement. Nebel e t a l . 48 concluded t h a t the r a t e o f

ozone d i s i n f e c t i o n is c o n t r o l l e d by mass t r a n s f e r , r a t h e r than contact time. Treatment w i t h up

to 20 ppm of ozone does not show a true ozone r e s i d u a l , i n d i c a t i n g t h a t the r e a c t i o n r a t e w i t h

carbonaceous m a t e r i a l s is f a s t e r than the mass t r a n s f e r step. Thus, in t h i s range, automatic

c o n t r o l by r e s i d u a l measurement is i m p o s s i b l e . However, a quasi-ozone r e s i d u a l , in the form o f

organic p e r o x i d e s , e x i s t s f o r measurable periods of time. The s u i t a b i l i t y of the peroxides as a

measure of d i s i n f e c t i o n is beinq i n v e s t i g a t e d .
No. i 23

Ward et al. 43 in their study of disinfectants applied to activated sludge effluent found

ozone to be neither acutely nor chronically toxic to those aquatic animals tested (P. promelas

and Daphnia magna). However, ozonated effluent often failed to meet the arbitrary standard of

200 fecal coliforms per |00 ml (lO00 total coliforms per lO0 ml) unless f i l t r a t i o n proceeded

ozone injection. Chlorination/dechlorinationhad a much better record in this respect. Ozone

dosage was limited to 8 ppm due to the capacity of the generation equipment.

Odor is reduced by ozonation through the oxidation of noxious compounds. Huibers et al. 38

reported virtual elimination of color, odor and t u r b i d i t y in t r i c k l i n g f i l t e r effluent using

ozone after chemical coagulation. Kirk et al.49 also reported odor and t u r b i d i t y reduction in

p i l o t plant studies of t e r t i a r y wastewater treated with ozone. Rosen50 believes that ozone for

odor control is becoming an established process as i t has been successfully used for a number

of years. Ozonation, unlike chlorination, is not e f f i c i e n t in reducing odors by preventing

anaerobiosis prior to secondary treatment. While ozonation would destroy many of the responsi-

ble bacteria, and restore more than a f u l l compliment of oxygen to the l i q u i d , the lack of re-

sidual would allow recurrence of the problem. Furthemore, ozone dosages sufficient to achieve

bacterial k i l l s in untreated effluent would most l i k e l y be uneconomical and d i f f i c u l t to attain.

48
Nebel et al. foundBOD5 levels to remain almost constant until 60 ppm ozone was added,

after which the BOD5 f e l l . COD levels, however, dropped in a much more regular pattern. Initial

increases in BOD upon ozonation have been reported by others. Those observations are explained

by the addition of oxygenated functional groups on previously nonbiodegradable compounds, pro-

ducing sites for microbial attack. COD is reduced by this oxidation, but BOD values are raised.

Use of oxygen feed gas results in treated effluent dissolved oxygen levels as high as 40 ppm.

With proper discharge, this surplus can be used to increase stream oxygen, thus p a r t i a l l y nega-

ting the adverse effect of BOD addition and eliminating the need for post aeration.

Specific contaminant removal from secondary effluents can be achieved in a two step pro-

cess, involving oxidation of reduced species and a frothing operation allowing removal by f l o -

tation. Ozonew i l l effectively convert cyanide to cyanate, which is readily biodegradable. 48

51
Gardenier reported that ozone reduces or eliminates organic pesticides by attacking carbon-car-

bon double bonds. Ozonehas also been shown effective on nonbiodegradable detergents, although

use of such has now largely been eliminated. Ozonationis not normally effective in removing

nitrogenous compounds, as carbonaceousmaterial is preferential.ly attacked.

 24 No. 1

Ozonation Problems.

As ozone technology f o r wastewater t r e a t m e n t is s t i l l in the stages of i n i t i a l develop-

ment, r e l a t i v e l y little is known about p o t e n t i a l problems. E f f e c t i v e n e s s o f ozonation is ham-

pered by excessive c o n c e n t r a t i o n s o f p o l l u t a n t s and v a r i a b l e f l o w s i t u a t i o n s . Wastes r e q u i r e

a t l e a s t secondary t r e a t m e n t to remove s u f f i c i e n t ozone demand. Unless extremely high ozone

dosages are a p p l i e d , incomplete d i s i n f e c t i o n and i n e f f i c i e n t removal o f odor, c o l o r and t u r b i -

dity result. Present ozonators are not able t o a c c u r a t e l y dose a wastewater v a r i a b l e , e i t h e r in

terms of f l o w or q u a l i t y . A p p l i c a t i o n must n e c e s s a r i l y be l i m i t e d to t r e a t i n g an e q u a l i z e d

f l o w or an i n t e r m i t t e n t s t a r t and stop o p e r a t i o n . The l a t t e r s u f f e r s from long g e n e r a t o r down-

times, as moisture accumulating in the a i r conduits must be d r i e d before r e s t a r t i n g . 3 The e f -

f e c t o f discharged ozonated wastewaters upon l o c a l a q u a t i c environments is s t i l l l a r g e l y un-

known. While Ward e t a i . 4 3 noted no t o x i c e f f e c t s on Daphnia or fathead minnows, they pointed

out t h a t c e r t a i n o t h e r studies i n d i c a t e t h a t u n d e s i r a b l e b i o l o g i c a l e f f e c t s could be associated

w i t h the ozonation of wastewater.

CONCLUSIONS

A review o f c h l o r i n a t i o n and ozonation p r a c t i c e makes c l e a r both the enormity o f the be-

n e f i t s a l r e a d y gained as well as the pressing need f o r s t i l l f u r t h e r achievement. The water

treatment industry will undergo g r e a t change as a d d i t i o n a l requirements and r e g u l a t i o n s appear

in response to newly recognized needs.

C h l o r i n a t i o n has been l a r g e l y r e s p o n s i b l e f o r the success o f d i s i n f e c t i o n . C h l o r i n e , as a

strong o x i d a n t , is also used to c o n t r o l t a s t e s and odors, prevent a l g a l growths, m a i n t a i n c l e a r

filter media, remove i r o n and manganese, destroy hydrogen s u l f i d e , remove c o l o r , c o n t r o l slime

growths in d i s t r i b u t i o n systems, r e s t o r e and preserve p i p e l i n e and well c a p a c i t y , s t e r i l i z e

3
water mains and o t h e r appurtenances, and improve c o a g u l a t i o n by a c t i v a t e d s i l i c a . In compari-

son w i t h ozone, c h l o r i n e shows a number of d i s t i n c t advantages. C h l o r i n a t i o n of p o t a b l e water

r e s u l t s in r e s i d u a l d i s i n f e c t i n g capability, p r o t e c t i n g s u p p l i e s from r e c o n t a m i n a t i o n in the dis

tribution system. C h l o r i n a t i o n is p r a c t i c e d at a much lower cost than o z o n a t i o n , and is much

more f l e x i b l e in a d j u s t i n g to f l o w r a t e and water q u a l i t y v a r i a t i o n s , which is due mainly to the

ease of process m o n i t o r i n g since s a t i s f a c t o r y techniques f o r c h l o r i n e a n a l y s i s e x i s t . I t is

known t h a t c h l o r i n e can r e a c t w i t h c e r t a i n organics to produce products t h a t are known to be

toxic or potentially c a r c i n o g e n i c to humans. The c o n c e n t r a t i o n s o f such products has u s u a l l y

been assumed to be below l e v e l s r e q u i r i n g concern, or at l e v e l s presenting less of a h e a l t h

No. i 25

threat than posed by alternative practices. Evidencehas not been provided to disprove this

b e l i e f , although research must continue.

The position of chlorination in wastewater treatment is far less secure. Sufficient evi-

dence has accumulated to show that chlorinated effluent has a negative effect on the receiving

water. Tests have shown that a f i n a l dechlorination step w i l l eliminate measurable effects.

However, dechlorination is not l i k e l y to a l t e r the net production of chlorinated organics.

Since much larger quantities of organic precursors are present in wastewater, the problem of

t h e i r production is far greater than with water treatment. Therefore, dechlorination cannot be

given f u l l approval as an acceptable solution until more is known about chlorinated organics pro-

duction and their implications. Cost considerations might also point towards a different means

of treatment, as chlorination-dechlorination is r e l a t i v e l y expensive.

Disinfection of potable water is the largest water related application of ozone. With a

higher oxidation potential than chlorine, ozone also shows improved taste and odor and color de-

struction. However,ozonation of potable water supplies appears to be i n f e r i o r in l i g h t of cur-

rent chlorination capability and f l e x i b i l i t y . While ozone is a rapid and effective disinfectant,

i t is both short lived and expensive. The benefit of maintaining residual disinfecting capabili-

ty has been demonstrated, and is a highly recommended practice. Where postchlorination is re-

quired to counteract this deficiency of ozonation the cost of treatment is further escalated,

with no demonstrable improvementover chlorination. Therefore, unless current chlorination prac-

tice is demonstrated to be harmful to human health, l i t t l e increased demand for ozonation of pota-

ble water supplies is l i k e l y . Although the cost of chlorine is rising rapidly, so is the price

of e l e c t r i c i t y for ozonation. Recognizingthe adaptability of the chlorination process, i t ap-

pears unlikely that problems identified in the future could not be solved before resorting to

abandonment of chlorine use.

The future of ozonation looks much more promising in wastewater treatment applications,

although experience has been limited to p i l o t plants. Ozonationhas been shown to be satisfac-

tory as a disinfectant of high quality secondary effluent, as well as successful in reducing

troublesome color and t u r b i d i t y problems. Cost estinlates appear to compare favorably with those

of chlorination-dechlorinationprocedures. Currently there is hope that future generating and

contacting devices w i l l see further improvement in r e l i a b i l i t y , adaptability and economy. The ex-

tent of such improvementw i l l prove c r i t i c a l . Furthermore,ozone use, l i k e that of chlorine,

26 No. I

must pass future tests dealing with effects on human health and the environment.

Acknowledgement. The research reported here has been supported in part by Grant No. 804594-01
from the U. S. Environmental Protection Agency.

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