245

The Science of the Total Environment, 18 (1981) 245--~261

Elsevier Scientific Publbhing Company, Amsterdam -- Printed in The Netherlandi

ADVANTAGES AND DISADVANTAGES OF Ci~HICAL OXIDATION AND DISINFECTION BY OZONE AND

CHLORINE DIOXIDE
F. FIESSINGER (I), Y, RICI~RD (2), A. HONTIEL (3) and P, HUSQUERE (I)

(I) Soci~t~ Lyonnaisc des E~ux, 45 rue Gortamber~, 75Ol6 Paris, France
(2) SociOc~ Degr~mont, B.P. 46, 9215f Suresnes Cedex, France
(3) Service de Contr~le des Eaox de in Villa de Paris, 144 avenue Paul Vaillant

Couturier,

75014 P a r i s , France

ABSTRACT
Ozone and chlorine dioxide present deflnite advantages and disadvantages o v e r
chlorination. Clll0rlnatlon , partlcularly for the removal of mmaonia and the maintenance of a d i s i n f e c t a n t

r e s i d u a l in the d i s t r i b u t i o n system has d e c i s i v e advan-

tages and w i l l be d i f f i c u l t to r e p l a c e . Ozone and c h l o r l n e dio.xlde seem to produce

fewer c a r c i n o g e n i c by-products but the r i s k f v r acute t o x i c i t y , e s p e c i a l l y from
the c h l o r i t e s which follow c h l o r i n e dioxide, is higher than with c h l o r i n e .
Chlorine dioxide and more p a r t i c u l a r l y ozone should be considered as u s e f u l
complements to chlorination, buc no strong oxidative treatment should be applied
before most of the organic matter has been removed.

INTRODUCTION
Comparison wi.th Chlor.~ne
The awareness of the p o t e n t i a l h e a l t h hazards created by the presence of h a l o genated compounds'in drinking water h a s l e d public authorities and water suppli&ra

to i n v e s t i g a t e a l l p o s s i b l e means o f . r e d u c i n g them, N ~ e r o u s s t u d i e s ~hroughout

the world (5) have led to the eonclusion t h a t high" c h l o r l n e d o s a g e s in wa[ers
c o n t a i n i n g organic r - e c u r a o r s should beabandoned. These waters, however, must be
\

d i s i n f e c t e d , and very o f t e n require, an o x l d a t l o n treatment for the',~emoval of

turbidity,

t a s t e or c o l o r . ' A l t e r n a t i v e s t o c h l o r l n e have t h e r e f o r e bepn sought,

and among t h e s e , c h l o r i n e dioxide and o~one are t h e ~ o s t

a~tractive:'~n~addltlon

to producing l e s s o x i d a t i o n b y - p r o d u c t s f : t h e y have a g r e a t e r o x i d i z i n g p o t e n t i a l
and seem to inactivate ba'c~erla and viruses more readily than chlorine, Several
\

e x c e l l e n t articles~ have a l r e a d y been dedicated tO the advan[ages and diaadvahtagea

o f ' t h e s e reagents ( $ , ' 8 , 9 , - ' 1 2 ) ~

T h e ' p r e s e n t p a p e r ' d o e s nOt at~ewpt-to present-"

any ne~ f i n d i n g s on o x i d a t i o n and d i s i n f e c t l o n , or to d i s c u s s the h e a l t h a s p e c t s

0048.969718II0000-00001502.50 1981 FJemvierScientific Publlshing Company

,24G
whlch n r u t r e a t e d elst, where ill t h i s sympoaltaa, but rnvrely t r i e s

to p o i n t out

~or0e vt~ry p r a ~ t l c o l

c o n c l u s i o n s about the use o f t h e s e d i f f e r e n t

surface water treatment process,

th~l~ may he h ~ l p f u l

oxidants

in a

to a g'ator t r ( , a t m e . t p l a n t

operator.
O x i d a t i o n and b i s i n g e c t i o n
I t is d i f f i c u l t

to separate

the o x i d i z i n g aa~d the d i s i n f e c t i n g

capacities.

Ozone is the s t r o n g e s t ok' the t h r e e o x i d n n t s ; the~ corses c h l o r i n e d i o x i d e and

finally

chlorine.

TIw g e r m i c i d a l e f f e c t l v e l ~ e s s g o e s , of c o u r s e ,

in the same o r d e r ,

In the c o u r s e of t h i s p a p e r the term~ o x i d a n t and d l s i n f e e t a ~ l t w i l l be used i n t e r changabty ~itl~

h o e e v e r , a p r e f e r e n c e f o r the l a t t e r

~hen i t is used in a f i n a l

unit procesg.
P o s i t i o n of Oxidat.ion 9ud. ~ i ~ i . n r s c s i o n

in the Treatmen._ t P r o c e s s

The e f f e c t o f an o x i d a n t i5 c l o s e l y r e l a t e d
i n tho o v e r a l l

t o the p o i n t a t v h i c h i t

is applied

t~eatment p r o c e s s . F i g u r e I sur~narizes the v a r i o u s p o s s i b l e p o s i -

t i o n s in a f a i r l y

cca~plete s u r f a c e ~ a t e r t r e a t m o . t p r o c e s s , The o x i d a t i v e r o l e

i s o~ c o u r , e d e c r e a s e d when the r e a g e n t i s i n t r o d u c e d at the end ~ the p r o c e s s .

Figure I also indicates

tl~e po.sslble c o m b i n a t i o n o f s e v e r a l o x i d a n t s .

l e n t sequence, f o r i n s t a n c e ,

is clarification,

An e x c e l -

ozonation, granular activated

with c h l o r i n e .

This g e n e r a l case

carbon (G,XC) f i l t r a t i ~ r t

and f i r t a i d i s i n f e c t i o n

o f w a t e r treatme,at ~ i t l

s e r v e as a b a s i s f o r the comparison o f tlie t h r e e d i f f e r e n t

oxidants,..

RAW
"

WATEH

----I

[ _ o,S'"'C],oN

i LxvoAT' oN

-J

POTABLE WATER
~ig.

l,,Poaltion

of o x i d a t i o n t r e a t m e n t s in a g e n e r a l . s u r f a c e

water treatment process,

24"1

llll(l

RAW WATER

I 8~AK_ POIWT" I

sl~.~O t!LTm,tmN I

/
-

~~--I

J,

.oi+~_t,t,,. J

i]-

i"_._= ,~L,,,!,o,
i ~~
(

LIW| N'I

"

l
LINI I1" 3

LINE I I ' l

Fig. 2. General |ay+out

~o-,,,j
I

I",o ., ,,L,,,,,o.
l
+,
PILOT
ll~fl N I

o( tli Horsang-sur-Seine r a t e r t r e a t m e n t p r o c e s s .

v._~'C,%LULP,I| Liae

F,lt I,f

[a,,.,,,..

Isdvstrmal L,ae

L r , l t t r I ~,ml=w J

+.i

gig. 3. C,nt -~ l a y - o u t o the Vigneux-sur-Seine water t r e a t m e n t p l a n t .

24B
.The

Horsan~ and.Vjgnet~ Experiments

Host of the results presented here come from the authors' experiments conducted

p r i m a r i l y at two p l a n t ~ t r e a t i n g

the w a t e r from the Seine in the P a r i s a r e a . The

general layout o f these two plants i s given i~ Figures 2 and 3.

The Norsang p l a n t has been u~ed f o r s e v e r a l y e a r s to s t u d y the e f f e c t
CoAC and, p r e c h l o r i n a t i o n ,
~ith it,

At the Vigneux p l a n t and on the p i l o t

of ozone,

a c t - u p which goes

s t u d i e s a r c p r e s e n t l y b e i n g made o n c h l o r i n e d i o x i d e and f u r t h e r r e s u l t s

will be p r e s e n t e d in the n e a r f u t u r e ,
~SE OF OXIDANT AS PRETREATHENTS
In a recent article (4) the outhors have discussed the various advantages and
d i s a d v a n t a g e s o f u s i n g c h l o r i n e as a p r e t r e a ~ n e n c ,

T h e i r main c o n c l u s i o n is t h a t

prechlorlnation should be abandoned, bu~ in order to control the final disinfectant

consumption and its residval by-products, granular activated carbon and possibly
ozone should be included in the treatment process. Abandonlng prechlorlnation,
bo~ever, creates plan~ operational problems which explain much of the reluctance
of o p e r a t o r s t o do so,

Stability
Ozone decomposes quickly in water (Figure 4) and thus has no lastlnq effect.

'l

Fig. 4. Decrease in residual ozone

with time - Seine water

O,
0 I.
O

.5

10

15

T
20 ~

Chlorir, e and c h l o r i n e d i o x i d e a r e c o m p a r a t i v e l y much more s t a b l e ,

Chlorine

dioxide, however, is very sensitive to,l~ght. Figure 5 represents the chlorine

dioxide and chlorlte concentrations in dark.(A) and light (B). The differences,
due only to clouds ~nd sunlight, are in R

to I ratio, which makes the residual

levet very difficult to control in open-air ciarifiers and filters.-In comparlson,

chlorlne~s fluctuations are only in a 20 Z.range. This L~I a major disadvantage
of CIO 2 and in many cases,' would be a'sutficicnt reason for not using it as a
pretreatment. One may object that the Wo~ks could be covered (th6y arep in fact,
in the Vigneux experiment)..but in that case the gro~th of algae, ~hlch is the,
most common reason for using preoxldation, could be e{ectlvely controlled and
the need for 102 pretreatmenC would be greatly reduced

249

Re,;du,t ewI doq| 'u| I I

F'~

to:,, I

./

~ L~t~., . ' ' ' ' ~ -

.,/

"e

O.S
0
Re|,dvJ

e f j'd,lnt

mill

0.!S
0

~
~ i ~~ "
1

:.~.L__

ttl |

',"

' * - - ' ' " - ~ - ~ ~4

.7

clot Ipphod m|ll

Fig. 5 .

Changes i n reaLdua! C10 2 and b y - p r o d u c t s .in the dark (A) and a t s u n l i s h l :

TABLE: I : A l g a l

cou~cs in w a t e r t r e a t e d wJl:h C12 and ClO 2,

TREATMENT,

SJ~tPLING
POINT '
1

RAW WATER

I 16.7.8ot 22.7.8oj,)o.7.8o
-

..I

OTAL ALGAL COUNT / ML.-

600

1 200

1 200

,L

OXYDANT- DCSE
PPM

CIO2

ClO 2 .i- CLARIFICATION

C] 2

3T

+ CLARIFICATION

C12

C10. + CLARJFJC.AT|ON
+ z SAND FILTRATION

CI
+2

liT

0.95
)6

}0

0
d,

+ CLARIFICATION
SANDFILTRATI~N

1.15

5.5
4.15

9."

33

21

(B),

250
C a n t r~l

A~o

An i m m e d i a t e r e s u l t

of eliminating

warm p , , r i o d - i s a p r o l i f e r a t i o n
In addition

to fouling

clarification

chloritle.

rapid

Chlorine

as chlorine
exactly

comparable.
later,

its

dioxide

instability

the

and f i l t e Y s .

g r o w t h may i n t e r f e r e

growth.

in T a b l e

with

One may o b j e c t

lower effectiveness
in s u n l i g h t

alternative

to

I - does not seem as efficient

that

But how can we c o m p a r e tl~em ? T h i s

The r e l a t i v e l y

greater

this

o z o n e c a n n o t be a v i a b l e

- as indicated
algae

during

runs.

disappearance,

in c o n t r J l l i n g

discuss
to

the filter

- especiltlly

in t h e u n c o v e r e d c l a r i f l e r s

t h e work~ c o n s i d e r a b l y

aL~d s h o r t e n

Because of its

preehlorination

of algae

the dosages

is a point

are not

~ h a t we s h a l l

o f CIO 2 may a l s o

be related

t h a t we h a v e ' ~ m e n t i o n e d e a r l i e r .

Clari fieation
I t h~s bgen shown (4)

the use of prechlorinatton

that

improves

the

turbidity

of water by some IO %. Chlorine dioxide seems to have a very comparable effect.

Ozone Itas b e e n p r e s e n t e d
tates

i r o n and m a n g a n e s e

with a high organic

( e l 2 and C10 2 a l s o ,

content

quenfclar/fication.
effect

as a good microflocculant

it

also

This effect

see table

enhances

the floc

ks s u ~ a r i z e d

o f o z o n e i s more i m p o r t a n t

if

(3).

It

4),

but in cases

formation

in Figure

a low c b a g u l a n t

of course

precipiof water

and the subse-

6 : the be:,.,ficia!

(under)

dosage

is applied.

This improvement of turbidity can be as high as 20 Z but will not generJflly

justify
ting

t h e use o f a s p e c i f i c

application

o f an e x c e s s

ozona~ion unit,
production

T h i s may, h o w e v e r , b e a n i n t e r e s -

capacity

- or off-gases

- o f an o z o n a -

tion unit used primarily for intermediate oxidation (see later), particularly
since the doses used for good clarification in pretreatment are generally small.
This effect

has also

b e e n shown f o r o r g a a i e

r e m o v a l (4 b i n ) .

3.0 ~
"
:\ k ~
p.'.
2,0
~
~,

1.0

~
CLARIFIED~WATER(NO O3]
_ _ . ' ~ " CLARIFIED WATER (IPPM 03l
FILTERED WATER ( NO 03 ]
,.--4-- FILTERED WATER (I PPM g3 )
. - - _

"'

.__.,

"i~'~l "+,,,,..,,,

' 'j . . . .

-,

.....

20
COAGULANT

"

40
DOSE-

u'
|0

PPM

I
Ill

WAC

Fig. 6, Effect of pre-0zonation o n water clarification. La S e i n e at Croissy, Ref. 3

9-81

E l i m i n a t i n g p r e c h l o r i n a t i o n causes n s l i g h t decrease In the f i l t e r s ' p r o d u c t i o n

c a p a c i t y . T hi s . of course, v a r i e s widely with tlm type of works, the f i l t e r

medium

and the filtration velocity, It seems (4) to cause a real pro'blem during the periods

o f peak f l o w - m r s only. This s h o r t e n i n g of the f i l t e r

runs is p a r t t y r e l a t e d to

the presence of plankton, and one may expect a l e s s e r e f f i c i e n c y of Chl ori ne d i o x i d e

,r.;'
and'ozone. Table 2 gives an example of filter runs with CI 2 and CIO2"Pretreatments
at Vi&neux, There is generally a hi&her headless build-upon

filters receiving

w a t e r . t r e a t e d with C102. On the o t h e r hand, the t u r b i d i t y of t h e ' . f i l t e r e d ' w a t e r

seems t o be a l i t t l e

, over ,
!

The use of ozone is inadequate because of its inability to control plankton,

TABLE 2 : Comparison of filter runs with CI 2 and CIO 2 pretreatment.
"

I-~c~:DLOS$

TURBIDITY

WATERCH

FTU

TIHE
.
. .

.,,

2.5

10

0.20

O.21

O,18

0.18

12

2k

~4

29

0.25

0,22 ~
L_

mml

48

75

62

0.18

0,20

7~

120

89

0.19

0.30

COAGUU~ff : ~ C ~O PPM - H25Ob : 8 PPH

CL2 : 7 PPH
CLO2 : ~ PPH
FILTRATIOH VELOCITY 5 H/H - SAND EFFECTIVE SIZE : O.95 t4q

B ~ c t e r i c i d a l and Vi~11icldal E f f e c t s
Although the main purpose of

pro-oxidation

is not t h e ' ~ n a c t i v a t l o n o f b a c t e r i a ,

iC does have some advantages as a bactericidQ.

[t provides\for a'to~g contact time,

makes possible a complete kill (if Sufficient resldual is

i .present)
.....
and
-: makes disinfection more r e l i a b l e .

Table 3 i n d i c a t e s t however~ t h a t ~ u f f l c i e n t c o n t a c t time

would exist even if these reagents were applled.toward the'end of.the .treatment

p r o c e s s . I t a l s o seems i l l o g i c a l t o t r y to k i l l b a c t e r i ~ and v i r u s e s i n the p r e l i mlnary s tag es of the process where t h e y a r e s t i l l

p r o t e c t e d b~ suspended s o l i d s ,

A particular effect of a pretreatment with CI 2 or ClO 2 is tha~..it stabilizes

the e v o l u t i o n of the s l u J ~

r e t a i n e d in the c l a r l f l e r ,

iIn s t a t i c c l a r i f i e r s

where

the sludge can be retained for several d~ys, the elimination of preoxidation with
Cl 2 or C102 may atimulat~ obnox~ous~fe~nentations,
or sedimentation disturbances,

resultlng in taste and odors

2~2

TABI,E 3
D i s i n f e c t i o n p r a c t i c a l conditions.
CLO 2

CL 2

BACTER I ClDAL
_,

03

O,! - 0 . 2 PPM =O,.1 - O,2 PPM 0.1 - 0 . 2 PPM

1 TO 2 bin
5 TO IOMN
IO TO I5 MN

.,.

VIRULICIDAL

O.~ - O.5 PPH

30 TO ~5 I,,t,I
"-

0 . 4 PPH

o . 3 - 0 . 5 PPH
30

FREE-RE~;[DUAL CCIqCENTRAT[ CNS

An~a~ja Removal

"

t!

C ~ l o r i n e breaks down a=mon~a and~ [orms ch[oramtnes ( b r e a k - p o z n t

~oe two o t h e r s o x { d a n c s , c h l o r i n e

II

theory,).
S ,

d~ox[de and ozone, are i n e f f e c t i v e ,

An~on~

can a~*o be removed biologically, bu~ when the water temperature drops below 5~;,
this'~turaL nitri1cation deereasoa'~rastlcally and the use of chlorlne may st~\t~
be nece~#ary. 1 c o u l d , however, be u~ed l a t e r in the treatment process ( a f t e r

clariic.ation or even activated carbon filtration), when most by-products ~yecurt

sots hav~ been removed.

Reac'tion'uith Organic H a t t e r
Table 4 summarizes the varous efects o the ~hree oxidants on organic matter,
in addition to other pollutants. As a general rule, chlorine dioxide and ozone
are more efficient than chlorine in removing taste, odors and color.

TABLE 4
Su==ary o the main eects of the v a r i o u s o x i d a n t s .
POLLUTANT .

AMMONIA

ORGANIC

CHLORINE

O-sLOeI NE
DIOXIDE

+4-

i~;

TASTE

4"

++

COLOR

-H.

4-

MATTER
THM '..FP

INCREASED
BIODEGRADAB| LI T~

OZONE
1 ++-b
O

253

. I f ; however, organlc, macter I s expressed as COT or even COD, tim i n f l u e n c e of pre-

oxidation on i t s c o n c e n t r a t i o n remains very smuli. The'decrease due to c h l o r i n e or

x

chlorine dioxide pretreatment is g e n e r a l l y lone than I0%, Ozone may have a g r e a t e r

~luence.

This organic m a t t e r removal may take place through s t r i p p i n g or enhanced

biodpgradatlon, but probably not through d i r e c t d e s t r u c t i o n .

\

.~

The~maJor problem c r e a t e d by t h c . r e a c t l o n - - c l , o x | d s n t s with organic m a t t e r i s the

formatio~ of by-products,

,\

..

Chtorine reacts vith'organiccoml~ounds and forms organol~aLogons. O these~ tri-

halomethanes (TllH~\are the most notorious and are the cause o~ the current contro~
versy over c h l o r i n e ~ee. Halomethanes, however, ere formed only when organic
precursors and f r e e chlorxne r e s i d u a l are bth present [ o r a ~ u f f i c i e n c c o n t a c t
ti~rT. R e d u e - / ~ e

throe f a c t o r s may In many. cases be a s a t l s f a c t o r y measure.

Once formed, however, halomethanes are virtually impossible to ellmlnace by sub-

sequent t r e a t m e n t s .
Chlorine dioxide is a s t r o n g e r oxidant and does noC seem to form c h l o r i n a t e d
by-products.-Figure 7 confirms what is already widely accepted : Cl0 2 does noC

produce TIiH, T h i s , . O f course, is true when c h l o r i n e dioxide is correctly prepared

and is not accompanied by an important c h l o r i n e r e s i d u a l .

/\

w,__!. ,m,~om~.o____~. , ^

,, J f - / - \ S
s('i

/ ~ " ~

.--o

g
1~
,
""
--

.-.

,
zo /

~il

15. /

~."~ , I

tu d
. ]
3 J

i_;~

--

-~~-

-~

=.

'-

I-

,n

;.

/I

m,

e~

-=_--

-:- -

n
.,.Jql4
u 3

,,o, wn,out

II ~
--

_-

I
PR[CNLORINATION
w ,,'.,,~-,,-u~-~
. -

"...----.*

ALONE

Z ._~_~%

PltlCES$ (LINE 2 ] AT MOP.SIN& (tO7S- t i l l

"ALONli PROCESS WITH CI 0 z PRETREATMEN!

'AT VllilI|UX [ 1 1 | 0 )

Fig. 7. Changes in chl'oroform c o n c e n t r a t i o n along treatment "process.

],

2~4

I t has been shown (9. I I ) , however, t hat when c h l o r i n e d i o x i d e iu p r e s e n t , c h l o r i n e ' s

tendency to form TIIH is'somewhat reduced. I t is thus g e n e r a l l y accepted t h a t c h l o r i n e
d io x id e g s n e r a t e s fewsr c a r c i n o g e n i c b y - p r o d u c t s than c h l o r i n e ,
Chlorites. As Jar as we kno~ at present, chloritea CCL02") are the chloriue
dioxide by-products of major concern. Recent studies (2) have suggested that thes~
i n o r g a n i c r e a c t i o n products may p r e s e n t a h i g h e r r i s k o acut e t o x i c i t y than c h l o r i n e
or

ozone.

Upon o x i d a t i o n with ozone, c h l o r i t e s form c h l o r a t e s ( I ) . Tim a f i n i t y o ClO2f o r ozone is such that no ozone r e s i d u a l can i x i s t

t o g e t h e r with c h l o r i t e ( F i g u r e ! S ) .

ChLorine d i o x i d e c o n s t i t u t e s an i n t e r m e d i a t e r e a c t i o n p r o d u c t between c h l o r i t e s and

c h l o r a t e s . When i t t~ used, the i n c r e a s e in ozone consumption due to the p r e s e n c e . o f
chlorites may thus be considerable (Figure 9). ~)e effect of chlorates on health is
still

v er y u n c e r t a i n , and i t seems p r e f e r a b l e to keep t h e ~ at the lowest p o s s i b l e ,

level.

pM: ?

; RIl.,ivll |Lid.at
mill

el0 I- iait,iI -~ 0.4B ~ 1 1

o.i
0,4
Q3'

~~N
.,:"los /t
*\, /

0.1.
Oll*l I#phll s | /

.o.6

o.a

~[g. 8. Changes in C102 and CI02~ r~idttals when ozone is applied.

Ozonatlon is not the o n l y t r e a t m e n t ~that i n t e r f e r e s

with chlorites

in' the t r e a t -

ment p r o c e s s . A c t i v a t e d Carbon decompd~es them. I t : 6 a s . a l ~ o . 6een suggested, but

never proven~ that when chlorites are presentt chlorine dioxide may reform in the
p r es en ce of f r e e c h l o r i n e , Thus, the presence o f c h l o ~ ' t e ' s ~n p r e t r e a t e d ' ~ a t e r has a a t r o n g ' I n X u , nee on ,
the design of the overall treatment process.

256

:I

"

2
)
4
OION[ OOSE APN.IEO - PFM
F i g . 9. Oaone de,mad v i t h (4) and without- ( 4 t ) Old 2 p r e t r e a t m e n t rtt Vigneux.
Table 5 shows tho changes in c h l o r i n e d i o x i d e and i t s . i n o r g a n i c

by-products along.

the t r e a t m e n t l i n e with ClO 2 p r e t r e a t m c n t a t Vigneux, C h l o r a ~ i n e c o n c e n t r a t i o n .

(produced by.excess chlorine r e s i d u a l )

is pretty stable

; ClO 2 and more p a r t i c u -

l a r l y Cl02- d i s a p p e a r upon o z o n a t i o n , They are moat p r o b a b l y transformed .intoV-

chlocates ( l ) which are not e l i m i n a t e d by C~C f i l t r a t i o n I and t h e r e f o r a ' r e m a i n in

the t r e a t e d w a t e r . Sampling p o i n t 6B i n d i c a t e s t h a t w i t h o u t , o z o n a t i o n c h l o r i t e s
a r e s a t i m f a c t o r i l y removed by GAC and a r e thus not t r s f i s o r ~ e d i n t o c h l o r a t e s .
upon f i n a l
_

ozonation.

SN4PLING
POINT

ii

5B

0.10

0.00

0.0

O.O4

1.06 0.88

0.84

CLO2

o'"

O.S7

0.34

CLO2-

0.03

2.~

2.S~

0.3O- O.11
~.~0 0.00

5.25

03

In

68

ili 'ii

TPEA'I'MENT

--CL 2

5A

O
O

0.~6-

o r d e r to keep i n o r g a n i c b y - p r o d u c t s . t o

c a r r i e d o u t a f t e r CAC f i l t r a t i o n .

'Oxidant c o n c e n t r a t i o n
a l o ~ the Vigneux t r e a t m e n t
p r o c e s s , after CI02
prctreatment

TABLE 5

O,
0

dULY ]O t
CL02
"' O ] I
II

1980 : k K . :
: h . t ~ PPH
: 2 PPPt
: 0 , 7 PPH

~O PPH

0.03'O

a ~!o/~um l e v e l o z o n a t i o n s h o u l d b e

T h i s , as ~e sh~11 see l a t e r ~ p r e s e n t s so~e

d i s a d v a n t a g e s and r e p r e s e n t s an a d d i t i o n a l

reas~

f o r not u s i n g CIO 2 as a p r e t r e a t -

meat.

Ozonation reaction products are still

relatively

unknoun. Epoxy b y - p r o d u c t s have

been suggeseed but no c l e a r i d e n t i f l c a e i o n of t~Lm has been made. Host o z o n a t l o n

P56

r e a c t i o n p r o d u c t s hav~ a c i d i c ,

k e t o n e s and a l d e h y d e groups and a r e thus p r o b a b l y

more blodegradablo. Ozone does not produce hslogenated compotmds, but in some cases

may increase the concentration in trihalomethano precursors (T]LH FP). This is indicated in f i g u r e 7, ~here ozonacion of prechlorlnated water increases the concentration
In l l l M .
INTERMEDIATE OXIDATION
We saw ( F i g u r e I) t h a t o x i d a t i o n could a l s o be a p p l i e d in the Middle o f the t r e a t meat p r o c e s s , a f t e r

cJariflcatlo~

and b e f o r e sand or GAC f i l t r a t i o n .

c h l o r i n e d i o x i d e in t h a t p o # i t i o n v o u l d s t i l l

p r e s e n t most o t the d i s a d v a n t a g e s

mentioned above. Ozone, on the o t h e r hand ( l l ) ~

It contributes

ption,

presents interesting

characteristics.

to the e l l m i ~ a t l o n of a d d l t l o n a l o r g a n i c s and t h e r e f o r e d e c r e a s e s the

load a p p l i e d to the GAC f i l t e r s .

Morsang i t

C h l o r i n e and

This removal ~ay be v e r y small i n terms of TOC. At

is o n ' t h e o r d e r of 5 Z. Ozone b y - p r o d u c t s can b e ' e l i m i n a t e d

and i f the raw w a t e r c o n t a i n s hu~ic ~ a t e r l a l s ,

Both can take p l a c e in the GAC f i l t e r s

sequence o z o n a t i o n

through a d s o r -

t h r o u g h b i o d e g r a d a t i o n as y e l l .

and have c o n t r i b u t e d to the s u c c e s s o f the

OAC f i l t r a t i o ~ .

There i s ~uch c o n t r o v e r s y o v e r t h e p o s s i b l e enhancement of b i o d e g r a d a t i o n by GAC

( B i o l o g i c a l A c t i v a t e d Carbon). S e v e r a l a u t h o r s (6) now b e l i e v e t h a t the same b i n d s g r a d a t i o n c o u l d be o b s e r v e d in f i l t r n t i o n

on n o n - a d s o r p t i v e m a t e r i a l s .

TOC removed through such b i o d e g r a d a t l o n ( p a r t i c u l a r l y

n a t i o n has l e f t
small i n m o s t

ments, more a c c u r a t e t h a n TOC, to e v a l u a t e

inactivates

viruses.

and f i l t e r s )

t~ ~evelop new o r g a n i c m e a s u r e -

even i n t h i s p o s l t i o n ,

it effeetlvely

I f o x i d a t i v e p r e t r e a c m e n t is abandoned, t h i s o z o n a t i o n f u r t h e r
I t ha9 a l s o been shown (4) t h a t t h i s s t r o n g o x i d a t i o n s t e p w i l l

reduce t h e f i n a l d i s i n f e c t a n t

demand and ~ake the w a t e r b o r e s t a b l e .

o z o n a t i o n thus a p p e a r s to be n o t m e r e l y an a l t e r n a t i v e

but a v e r y s p e c i f i c

remains

t h i s " A s s i m i l a b l e O r g a n i c Carbon".

a d v a n t a g e o f o z o n a t i o n is t h a t ,

ensures d i s i n f e c t i o n .
lnter~ediate

the absence of p r e c h l o r l -

room f o r p r e v i o u s b i o d e g r a d a t i o n i n the c l a r l f i c ~

c a s e s , R e s e a r c h e r s (b) have thus t r i e d

An a d d i t l o n a l

if

The amount o f

to c h l o r i n a t i o n .

and o o m p l e m e n t a r y o x l d a t l o n t r e a t m e n t .

FINAL DISINFCTION
Germicidal E f f e c t i v e n e s s
p

A f i n a l g e r m i c i d a l t r e a t m e n t has to be a p p l l e d to the w a t e r b e f o r e ~t l e a v e s the

plant.

This t r e a t m e n t c a n n o t p r e v e n t a c c i d e n t a l p o l I u t l o n i n the n e t w o r k , but does

prevent its

d i s s e m i n a t i o n . A s~a~11 d l s i u f e e t a n t

m e a s u r a b l e g u a r a n t e e of the p o t a b i l i t y
If both bactericidal
final stage,

sufflcieut

and v l r u l i c i d a l

residual also constitutes

an e a s i l y

of the w a t e r ,

t r e a t m e n t have to be c a r r i e d out ac t h i s

c o n t a c t time must be p r o v i d e d ( r o u g h l y one hour w l t h s t o l e -

r a b l e r e s i d u a l c o n c e n t r a t i o n - see Table 3) b e f o r e the w a t e r l e a v e s the p l a n t .

necessitates

the c o n s t r u c t i o n o f r e s e r ~ o i Y s .

ThJ~

257
~.tnb i li_ty

FLnnl disinfectant h a s , t o be quite s~able. ?his eliminates ozone, w;..

blodegrad~blQ m a t e r i a l s ,

r~duc~s

stimulatln8 blolozical " a t e r g r o w t h " i n tlle distr,,

!,~,

network.
dioxide eeems to be more s t a b l e

Chlori,e
disln~ectunt

demands o f b o t h . ( i E ' t h o

than cl~lorlne - F i g u r e

10 - ,

p r e v i o u s t r e a t m e n t s were s i m i l a r

b u t th~

to chose a p -

plied at Vi~ neux or Horsang)'remain at a very reanonablc level.

0.3.
i

c,to,,,,
0.2.

/..,~~
CHLORINEOlOXlO|OI$1NF[CTION
//./*'-:" ~-O,MIkND ,)LP,c.SS[BIN ,QUWAL~"T~tRO,t,[
/.//
X oiM,N, EX.ESSiO W,,.'O,mOR,NEreX,O,
TIME- HDUA$
_

--

..

,'0
Fig.

_.

,q

--

2o

i,

lO. Final disinfectant demand, Vlry Chatillon, march 1980.

MeaSurement

This raises

t h e p r o b l e m of m e a s u r e m e n t , C h l o r l n e ' d i o x i d e and the v a r i o u s o x i d a n t s

:
d
which 8 o wi~h i t , a r e r a t h e r d i f i c u l ~ to measure w i t h p r e e l s l o n - ( 7 ) .
The c o m p a r i s o n
q

O~ chlorine on one hand with on the othQr, a combination of Cl02,:chlorites,

chlorine

a~d chlora~Ines is somewhat difficult. It thus seems more practical to speak in terms
o "equLvalent chlorine" expressed n vol~e

(drops) Ofreducins,ageut-(method

~ith

KI and sodium thiosulfate or phenylarslne oxide), than in weisht of dlsinfectant. The

dificulcy in measurin 8 ClO 2 residual where its concentration should be a~ccurately
controlled is s,notlcesble d l s a d v a n c a g e o~ this reagent.
Taste and Odor~
It is commonly accepted that chlorlne dioxide removes tastes and odors more
efficiently than chlori~e,:ThisLs~ndeed

true for phQnoliC tastes,:C~iorifie

dioxde, however, seems inc,~Fableof removing earthy.(geosmln

or MIB} tastes.

This is shuwn.inlFigure II. In bothca~es due to res~dual"dsi6fectant,".'Isappears

below 0.I ppm.

258

i,

'

|"

Z/

~3

"

o ,:H,.o,,,,.

CHLORINEOIGXIOE

E,
!

0.1

O,Z 0,3 0,4 0.$ 0,$ 0,7 O,I

FREERESIDUALDISINFECTANTIN PPM 'EQUIVALENTCHLURINE

Fig. II. Comparison o f tastes due to chlorine and chlorine dioxide. Vigneux. m.~rch 1980
(TON a r e a v e r a g e s f o r a p a n e l ' o f , slX p e r s o n s ) .
Because the s t a b i l i t y

o f t i e 2 i s somewhat g r e a t e r

than t h a t of Cl 2, the use o f an

excess CIO 2 residual, in "comparison with the same dosage of chlorine, may increase
appreciably

tlie~eust'0mers'complalnts, ' Figure

12 i l l u s t r a t e s

this

schematicalty

the area (and the number of customers) getting a ~Ibad-tasrlng~' uater is much larger
w l t h ClO 2 t h a n w i t h c h l o r i n e when d o s a g e s w i t h more than 0, I ppm r e s l d u a l , " a r e
~ppllcd.

/ZONEWITHOUTFREEFlESIOUAL----~~x**.

j /~o TASTE

]/

'

ZONEWITHEXCESSFREE

O 35
CHLORINE
Fig.

10

NI,

.l

%,

',

O 3

3|

CHLORINE DIOXIDE

12. T h e o r e t i c a l e v o l u t i o u 0 Eree r e s l d u a l d i s i n f e c t a n t i n the d i s t r i b u t i o n

s y s t e m . Comparison between c h l o r l n e and c h l o r l n e d i o x i d e ,

159

ADDITIONAl, ADVANTAGESAND b[SADVA.'~TAGES

Figure 13 sum~arlzes the various advantages of the three oxidants. Several o t h b r
but comparatively less importr.nt ~eatures oI~ the three d i s i n f e c t a n t s may he considered
as advantages or disadvantage~. 'r'h,e r e l a t i v e t n d e p o n d e n c o
of chlorine dioxide germicidal e f f e c t from pH changes is, i'or instance, very*oten presented sO a n advantage.
~oo r

Fig. 13. A summary of the advantages

of the three oxldan~s.
Alillnt ildeail

Chilli

~, ,-..;. ,,..

-., .,,:'. ~'..

,.~

OIsne

Oios,/ile de chlore

~sclillss
VifH

Autf|| p|thog|a|#
~ ' Slmln|nc|

"~'; t~,/'./., .:. ',

Absnc. o f

THM
Qoits st a.dluf|

||f it,Ha`
NH44

,Gr_o_i~nd ~/_a_t_e_r_Tr_eatment

The example that has been presented of a r a t h e r sophisticated surface water t r e a t menc process does not by any means represent the best process for a l i eases requiring
treatment by oxidation. In the case of ground waters, with a l i t t l e organic content
but wlth iron and more p a r t i c u l a r l y manganese in high concezltration, i t would ~e
preferable to use ozone esther than chlorlne or chiorlne dioxlde.
Water with phenolic t a s t e s sh0~Id be ~reeted*with chlorine diozlde (or ozon0)~
hot not with chlorine.
~ost ground r a t e r s with a low 0rganlc content could, h~aever, be ~erely t r e a t e d
with a small chlorine dosage.
and Operati~na!'C6nslderations
Chlorine is c e r t a i n l y the most cmnxnonly used chemical in water treatment, In i t s
l l q u l f i e d gas form. i t r e p r e s e n t s a dangerous prod'uc't and s t r i n g e n t Safety requxremeritsare "needed for i t s storage and'handlln8'. I't can ai'so be Used in t h e ~ f o m o f
hypochlorite's, vhich are much e a s i e r tO manipulate but r e s u l t i n ~igher Co's~. Dosing
C~sc

equipment for chlorine is slmpler and e a s l e r ' t o ~ o p e r a t e .

260

C h l o r i n e d i o x i d e I s p r e p a r e d on s i r e ,
w i t h c h l o r i n e gas o r h y d r o c h l o r i c
arise

as w i t h c h l o r i n e ,

through the r e a c t i o n

acid.

of sodiu~ chlorite

In the f o n a e r c a s e the same s t o r a g e p r o b l e m s

but an e~ergency c h l o r i n e g a s s u p p l y i s a v a i l a b l e

if the

dioxide g e n e r a t o r b r e a k s do~n. T h i s g e n e r a t o r ~ust be o p e r a t e d under a l m o s t s t o e chlc~aetrlc conditions

to avoid an e x c e ~ s o f c h l o r i n ~ o r c h l o r i t e .

difficult

CI02 g a s i s e x p l o s i v e and s a f e t y

to a c h i e v e .

s t o r a g e of C]O2 c o n c e n t r a t e d

solutions.

The r e a c t i o n

d e v i c e s must be used in the

of c h l o r l t e

a c i d i s a l s o e x p l o s i v e and t h e s e c h e m i c a l s s h o u l d be k e p t a p a r t .

efficiency

This is genera]Iv
~Itb cQncentrated
In a d d i t i o n

(up to 90 ~ w i t h ~ e i d and 95 ~ ~ i t h CI2) . t h e p r e p a r a t i o n

acid presents

to lo~er

vith hydrochlorlc

this disadvantage.

~zone~ o r ~ a t h e r o z o n a t e d a i r i s a l s o produced on ~i~e by p a s s i n g a ~ry a i r

b e t v e e n t~o e l e c t r o d e s
total

under a p o t e n t i a l

equipment Cair p r e p a r a t i o n ,

stantlal

capital

and o p e r a t i o n a l

d [ f ~ e r e n c e of 15,000 to 20,000 v o l t s .

ozone g e n e r a t o r ,

c o n t a c t chambers) r e p r e s e n t s

of the d i f f e r e n t

The
sub-

co~ts.

T a b l e 6 g i v e s an e s t i m a t e ~or the P a r i s a r e a o f the ~o~al c o s t s

cap~tal)

flo~

disinfection

treatments

used in a f i n a l

(operational

~tage. This cost

gives a c l e a r a d v a n t a g e to c h l o r i n a t i o n .
TABLE 6

Average c o s t s of c h l o r i n e , ozone
and c h l o r i n e dioxide t r e a t m e n t s .

O.}

O,J

0.4

~'

b I

xO

r.r ,, no"~.p~,...I

COSCLOS10N
(1) There does not seem to be a d e 1 n i t e s u p e r i o r i t y
over chlorine.
be c o n t r o l l e d
(ii)

Prctreat~ent

m e c h a n i c a l l y by c l e a n i n g a n d / o r c o v ~ r l n g t h e works.

Chlorine still

cases absolutely
(lil)

presents

t h e a d v a n t a g e o f removing aa~on~a and m i g h t be in some

necessary.

Ozone f o l l o v e d by GAC f i l t r a t i o n

(iv) Chlorine,

may ~ a v e a p o s i t i v e

by-products

natives

tree,eat

dlslnfectant.

t o a minlmu~ l e v e l ,

i n the l o n g term ~ i s the use of GAC. l ~ n y p l a n t s ,

introduce this

effect.

a t d o s e s b e l o ~ 0 . 3 pp~ may be k e p t as ~ f l n a l

I n o r d e r to r e d u c e c h l o r i n a t i o n
-

of ozone o r c h l o r i n e d i o x i d e

~ i t h an o x i d a n t should be a v o i d e d and a l g a e growth c o u l d

however, w i l l

the b e s t s o l u t i o n
not be a b l e t o

o r s e v e r a l y e a r s . Ozone and CIO 2 may t h u s be u s e d as a l t e r ~

to c h l o r i n e ~ b u t o n l y f o r an i n t e r i m p e r i o d o f t i m e .

261

REFERENCES
I

Y. Richard and L. Braner, I n t e r f e r e n c e Dioxyde de Chlore - Ozone en Traitement

d'Eau de Consommation, Congr~s A,G.H.T.M., Strasbourg, octobre 1980
2
R.J. Bull, Health E f f e c t s of A l t e r n a t e D i s i n f e c t a n t s and t h e i r Reaction Products,
J.A.N.N.A., 72 (may 1980), 299-303
3
F. F i e s s l n g e r , J . H a l l e v l a l l e and A. A l l i z a d e h , E f f e c t F l o c u l a n t d~ l'Ozone,
I n t e r n a t l o n a l Ozone I n s t i t u t e Conference, Nice, j a n v i e r 1979
4
F. F i e s s l n g e r and A. H o n t l e l , Case Studies for the Abandor~ent of P r e c h l o r i n a t l o n ,
A.N.N.A. Annual Conference, A t l a n t a , june |980
4b~s . Richard and P. Blue, Ozone Pretreatment of Drinking Water, International
Ozone Instltuce Symposium, Los Angeles, may 1978
5
N. K~hn and H. Sonthelmer, Precedes d*Oxydation Appliques au Traltement de l ' E a u
Potable. Karlsruhe 78, Rarlsruhe 1979, p. 854
6
J. Van der Kooij, Processes during B i o l o g l c a l Oxidation in F i l t e r s , g a r l s r u h e 7B,
( r e f . 5), p. 774
7
N. Hasschelein, Progr~s de la Chimie du Bioxyde de Chlore, G~nle lndustrle, G~nie
Chimique, 97, I Janv, 1967, 49-61 et 97-3, fev. 1967, 346-354
8
C. Gomella e t P. Husqu~re, La VAslnfection par le Chlore, l'Ozone e t le Vloxyde
de Chlore, 13e Congr~s A . I . D . E . , P a r i s , s e p t . 1980
9
R.G. Rice and J.A. Cotruvo, Ozone/Chlorine Dioxide Oxidation Products o f Organic
Haterlals, Proceedings of I , O , I , Conference, Nov. 1976, p,.487
]0
Y. Richard and L. Brener, Disinfectants and Equipment for Disinfection, Internatlonal Water Conservancy Exhibition, Jonk~ptng, sept. 78
11
Y. Richard and F. F i e s s i n g e r , Emploi Compl~mentaire de l'Ozone et du Charbon
Actif, 1.0.1. Conference, Paris, may 1977
12
C. a p i j a k l e , ICx f o r H20, Water and Wastes Engineering 15, may 1978, p. 33-37
.