OSE 13. Influence of Hydrodynamics on Giardia Cyst Inactivation by Ozone. Study by Kinetics and by "CT" Approach

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Influence of Hydrodynamics
on Giardia Cyst Inactivation
by Ozone. Study by Kinetics
and by “CT” Approach
M. Roustan , Z. Stambolieva , J.P. Duguet , O.
Wable & J. Mallevialle
a
Département de Génie des Procédés
Industriels, INSA , Complexe Scientifique de
Rangueil, 31077 Toulouse
b
Département de Génie des Procédés
Industriels, INSA , Complexe Scientifique de
Rangueil, 31077 Toulouse
c
Laboratoire Central de Recherche , Lyonnaise
des Eaux-Dumez, Avenue du Président Wilson,
78230 Le Pecq
d
Laboratoire Central de Recherche , Lyonnaise
des Eaux-Dumez, Avenue du Président Wilson,
78230 Le Pecq
e
Laboratoire Central de Recherche , Lyonnaise
des Eaux-Dumez, Avenue du Président Wilson,
78230 Le Pecq
Published online: 23 Jul 2008.
To cite this article: M. Roustan , Z. Stambolieva , J.P. Duguet , O. Wable & J.
Mallevialle (1991) Influence of Hydrodynamics on Giardia Cyst Inactivation by
Ozone. Study by Kinetics and by “CT” Approach, Ozone: Science & Engineering:
The Journal of the International Ozone Association, 13:4, 451-462, DOI:
10.1080/01919519108552282

To link to this article: http://dx.doi.org/10.1080/01919519108552282

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RESEARCH NOTE

Influence Of Hydrodynamics On Giardia Cyst Inactivation


By Ozone. Study By Kinetics And By "CT" Approach
M. Roustan1, Z. Stambolieva1, J.P. Duguet2, O. Wable2 and
J. Mallevialle2
Downloaded by [New York University] at 14:52 07 January 2015

1
D6partement de G6nie des Procddes Industriels, INSA,
Complexe Scientifique de Rangueil, 31077 Toulouse
2
Laboratoire Central de Recherche,
Lyonnaise des Eaux-Dumez,
Avenue du President Wilson, 78230 Le Pecq

Received for Review : 21 March 1991


Accepted for Publication : 2 May 1991

This Research Note deals with the problem of providing appropriate disinfection
from one of the most resistant microorganisms (the Giardia cysts) while trying to
provide a more strict and logical approach to the "CT" concept. A further
discussion of the U.S. Environmental Protection Agency (EPA) disinfection
requirements in accordance with the kinetics and hydraulics of the ozonation
process will be made in order to reconsider the definition of detention time. The
main objective is the comparison of two possible approaches for determination
of the disinfection conditions. The first implies consideration of the kinetics and
hydraulics of the ozonation process. The second is based only on the hydrody-
namics data and the use of an additional hypothesis known as the concept of the
"CT" value.

Concept Of The "CT' Value

The concept of the "CT' value was proposed by EPA to assure the attainment of
primary disinfection at a minimum cost. The "CT" values are determined as the
numerical product of the concentration of residual disinfectant "C" (mg/L)
multiplied by the time, T (min), during which the disinfectant is present. This
time "T" is not equivalent to the hydraulic residence time T = V/Q (where V is
the volume of the contactor and Q is the flow through this contactor) and should
be corrected by a factor determined through tracer studies to take into account
the residence time distribution curve.

451
452 M. Roustan et al.

To determine the detention time, one has to perform a tracer study at several
flow rates. LiCl can be used as the tracer, and it can be injected either
according to the "pulse" method (the response is the "C" curve) or according to
the "step" method (the response is the "F' curve) (1). The determination of
detention time is made from the plot of the "F' curve versus time.

The "T" value, chosen by the U.S. EPA (1989) is the time corresponding to F =
0.1. It means that 9O%, of the water passing through the contactor will have a
residence time greater than or equal to "T".

The detention time "T" is related to the residence time of a given contactor (T =
V/Q) by the single linear expression: T = a.r, where a is a coefficient which
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depends on the hydraulic behavior of the contactor and can have values between
0.1 and 1 [0.1 for a single completely stirred tank reactor (CSTR) and 1 for the
plug flow reactor, which are the two ideal cases]. In Tables 1 and 2 are given the
values of a for several models, as well as the expressions of the F curve versus
normalized contact time <P = t/r.

TABLE 1. VALUES OF T/T RATIO FOR DIFFERENT HYDRAULIC


MODELS
Hydraulic Model a
1CSTR 0.1
3 CSTR 0.36
4 CSTR 0.43
5 CSTR 0.48
6 CSTR 0.52
8 CSTR 0.58
Plug Flow 1

Tables 3a, 3b, and 3c contain data presented by the U.S. EPA (5) for CT values
to provide inactivation of Giardia cysts with chlorine, ozone, chlorine dioxide, and
chloramine (Table 3a), with ozone (Table 3b) and inactivation of viruses with
ozone (Table 3c) and cited by Rice (2).

The Kinetics

The kinetics of the disinfection of microorganisms are complex, owing to a


number of factors influenced by the type of organism, disinfectant and the
environmental conditions, such as pH and temperature. In this paper, we shall
consider disinfection with ozone as it emerges being the sole primary disinfectant
that is capable of providing rapid disinfection of Giardia cysts, viruses and
bacteria without generating halogenated products (in the absence of bromide ion).
The lowest "CT1 value reveals ozone as the most effective primary disinfectant.
GIARDIA CYST INACTIVATION - KINETICS AND "CT" APPROACH 453

TABLE 2. "F' FUNCTIONS FOR DIFFERENT HYDRAULIC MODELS


Model Expression of "F1 Curve F(<P)
1CSTR F ( 0 ) = 1 - exp(<Z>)
JCSTR
F(<J>) = 1 - exrf-JflEwy-Va-D!
i-i

Plug Flow F(0) for J CSTR with J -* », or F(0) = 1


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TABLE 3a. CT VALUES FOR 99.9% INACTIVATION OF Giardia CYSTS


(mg/L-min)
Disinfec- PH <1- 5-C 10'C 15'C 20-C 25°C
tant C
Free 6 165 116 87 58 44 29
Chlorine
at 2 7 236 165 124 93 62 41
mg/Lb 8 346 243 182 122 91 61
9 500 353 265 177 132 88
Ozone 6-9 2.9 1.9 1.43 0.9S 0.72 0.48
Chlorine 6-9 63 26 23 19 15 11
Dioxide
Chlor- 6-9 3,800 2,200 1,850 1,500 1,100 750
amine
(pre-
formed)0

The inactivation data are presented commonly in a form of "survival curves",


which are semi-log plots of survival ratio vs contact time. Survival curves for
inactivation of cysts by ozone in batch reactors were found to be of "convex" type,
consisting of an initial "shoulder" followed by a linear region. Similar configura-
tions have been reported for cyst inactivation with chlorine, chlorine dioxide and
for other disinfectant-organism combinations. Thus, the "CT' concept is a
simplified equation that derived from the early work of CHICK and WATSON
and is more correctly expressed as:

k = CnT

It is based on the Van't Hoff equation used for determining the nature of
chemical reactions in which the value n determines the order of the chemical
reaction. The value of n is very important in determining the degree to which
extrapolation data from disinfection experiments is valid.
454 M. Roustan et al.

TABLE 3b. CT VALUES (mg/L-min) FOR INACTIVATION OF Giardia


CYSTS BY OZONE
Logs Of Temperature, °C
Inactivation
< 1 5 10 15 20 25
0.5 log 0.48 0.32 0.23 0.16 0.12 0.08
Hog 0.97 0.63 0.48 0.32 0.24 0.16
1.5 logs 1.5 0.95 0.72 0.48 0.36 0.24
2 logs 1.9 1.3 0.95 0.63 0.48 0.32
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2.5 logs 2.4 1.6 1.2 0.79 0.60 0.40


3 logs 2.9 1.9 1.43 0.95 0.72 0.48

TABLE 3c. CT VALUES FOR OZONE INACTIVATION OF VIRUSES


(mg/L-min)
Logs Of Temperature, °C
Inactivation
< 1 5 10 15 20 25
2 logs 0.9 0.6 0.5 0.3 0.25 0.15
3 logs 1.4 0.9 0.8 0.5 0.4 0.25
4 logs 1.8 1.2 1.0 0.6 0.5 0.3

If n = I, the "CT" value remains constant regardless of the disinfectant concentra-


tion used (C and T are of equal importance in determining the inactivation rate).

If n > 1, the disinfectant concentration is the dominant factor in determining the


inactivation rate.

If n < 1, the contact time is more important than C.

Using the data collected by the U. S. EPA and cited in Tables #a, 3b, and 3c
concerning the inactivation of Giardia cysts by ozone, it is possible to show that
this process has simple first order kinetics which can be expressed by the
equation:

N/No = e k t

where: k = n = 1
A = 1.47 x 10" (L/mg.min)
E/R = 6834 (I/-K)
GIAKDIA CYST INACTIVATION - KINETICS AND "CT" APPROACH 455

The apparent activation energy is about 13700 cal/mole, which is almost twice the
value reported by WICKRAMANAYAKE and SPROUL (3) for the inactivation
of Naegleria gniberi cysts by ozone.

If In (N/No) = f(t) is plotted, a bundle of lines of negative slope which increases


with temperature is obtained. The slope is ICQ (see Table 4).

TABLE 4. KINETIC CONSTANT DEPENDANCE ON TEMPERATURE


T, -C ko, L/mg.min
5 3.6
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10 4.8
15 7.3
20 9.6
25 14.4

Kinetics And Hydraulics Considered Together

A completely rational basis for contact chamber design requires a relation


between the kinetics of the disinfection reaction and the distribution of residence
times, as well as a means of estimating the distribution of residual times for a
proposed contact chamber design.

The kinetic equation presented just above had been established in a batch
reactor. To obtain the mean conversion in the entire contactor, one has to apply
the segregated flow model. Using the concept of a segregated flow system, the
fraction of bacteria remaining after reaction will be the sum of the batch reactions
of all small aggregates:

Wo =

where: No is the initial concentration of Giardia cysts


N is the current concentration of Giardia cysts
E(0) is the distribution of the normalized residence time
T is the residence time of the contactor
(N/N0)b is the conversion in batch reactor
N/No is the mean conversion in the entire contactor
Thus, if tracer information for a given contactor, as well as the kinetic data for
a batch system, are available, the behavior of this vessel as a chemical reactor can
be determined and the corresponding mathematical model to calculate the total
inactivation used (Table 5).
456 M. Roustan et al.

TABLE 5. EXPRESSION OF THE COMPLETE CONVERSION FOR


DIFFERENT TYPES OF REACTOR BEHAVIOR
Reactor Model Expression of Total Inactivation, X
1CSTR 1 - X = N/Nn = 1/(1 + kr) T = V/Q
J
J CSTR J = 2,N 1 - X = N/Nn = 1/(1 + krf) T, = T/J
Plug Flow 1 - X = N/No = exp(-kr) T = V/Q

Thus, if the temperature and the concentration of residual disinfectant are given,
it is possible to calculate the true contact time necessary to provide 1-, 2-, 3- or
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4-logs of inactivation of Giardia cysts. The value of r thus obtained then is


compared to the value given by the CT tables.

Results and Discussion


Keeping in mind that the requirements for the water treatment process to provide
primary water disinfection are 3-logs (99.9%) inactivation of Giardia cysts and 4-
logs (99.99%) inactivation of enteric viruses, it is now possible to make the choice
of the chemical reactor. The calculated values of contact time using the kinetic
equation of inactivation and the CT tables are presented in tables 6 and 7.
Comparing the values of contact time obtained by the disinfection kinetics, (r a )
and the "CT" concept (T 2 ), it can be readily deduced that only the cases in which
T < T or T = T are
i 2 i 2 °f interest, otherwise the inactivation requirements are not
satisfied. The contact time should be at least equal to the time required by the
true kinetics in order to obtain the desired inactivation effect. It may be even
greater; in this case an additional security is assured.

A deeper analysis of tables 7 and 8 allows us to divide each of them into two
parts and to make the following important conclusion :

TABLE 6. VALUES OF NORMALIZED TIME 4> = T/r FOR DIFFERENT


VALUES OF THE "F 1 FUNCTION
F = 0.05 F = 0.10 F = 0.20
1CSTR 0.05 0.1 0.22
2 CSTR 0.1 0.2 0.4
3 CSTR 0.21 0.36 0.47
4 CSTR 0.32 0.43 0.58
5 CSTR 0.41 0.48 0.65

The "CT' concept in general is quite a simple and convenient method to


characterize the contact time in the disinfection contactors. However, this
approach can be applied without any risk for committing an error only if the
GIARDIA CYST INACTIVATION - KINETICS AND "CT" APPROACH 457

following two conditions are satisfied (those parts of tables below the main
diagonal):

1. The hydrodynamic behavior of the contactor is represented by at least 3


CSTRs in series,

2. The required inactivation provided by ozone is comparatively low (less than


3-logs inactivation of Giardia cysts).

In all other cases (those parts of tables above the main diagonal), the values
of contact time obtained by the "CT" approach should be considered with caution.
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TABLE 7. VALUES OF CONTACT TIME (min); C = 0.1 mg/L; T = 10 • C

Inactivation 68,38% 90% 99% 99,90% 99,99%


model kinetics C l kinetics CT kinetics CT kinetics CT kinetics CT
•tl •a tl T2 Tl 12 Tl T2 Tl T2

1 CSTR 4,51 23 18,8 48 206.3 9$ 143 20831: t93

3 CSTR 2,92 6.39 7,2 13,3 22.8 26,4 56,3 39,7 53,6

4 CSTR 2,78 5,35 6.5 11,2 18 22,1 3Sf5 33,3 75 <Wr9

5 CSTR 2,70 4,79 6,1 10 15,8 19.8 3t . 29,8 55.2 40,2

6 CSTR 2,64 4,42 5,8 9,2 14.4 18,3 27 27,5 45,4 37,1

PLUG FLOW 2,30 2,30 4,8 4.8 9.5 9,5 14,3 14.3 19.3 19.3

Actually, any conventional treatment plant with filtration and sedimentation steps
can take 2.5-logs credit for Giardia cyst inactivation (0.5-log for the sedimentation
basin and 2-logs for the filtration step) (2). Therefore, the disinfection step, using
ozone, will only have to provide 0.5-log of Giardia cyst inactivation1. It can be
seen in Tables 7 and 8 that for 0.5-log inactivation (68.38% inactivation of Giardia

1
Compared to the inactivation of virus, it can be noticed that for the same
conventional treatment process, ozone disinfection must provide 2-Iogs of virus
inactivation (since the filtration and sedimentation are credited with 2-logs
inactivation). However, the CT value for 2-logs of virus inactivation usually will
be higher than the CT value for 0.5-log Giardia cyst inactivation.
458 M. Roustan et al.

cysts), the values for the contact time given by the CT approach (T 2 ) are largely
superior to those calculated with the kinetics equation (TJ). In this case there is
no risk of undervaluation of the disinfection effect when applying the CT concept.

TABLE 8. VALUES OF CONTACT TIME (min); C = 0.4 mg/L; T = 10 • C

inactivation 68,38% 90% 99% 99,90% 99,99%


model kinetics CT kinetics CT kinetics CT kinetics CT kinetics CT
il 12 il 12 il 12 il 12 il t2
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1 CSTR 1.13 5.75 6,7 12 51.6 23,8 52O.S 35,8 6208 48.3

3 CSTR 0.73 1,60 1.8 3.3 5.7 6,6 14,1 9,3 32,T 13,4

4 CSTR 0,69 1.34 1.6 2.8 4,5 5,5 9,6 8.3 183 • 11.&

5 CSTR 0,67 1,20 1.5 2.5 4 5 7& 7,5 133 10,1

6 CSTR 0.66 1,10 1.4 2.3 3.6 4,6 6.8 6.9 11 9,3

PLUG PLOW 0.58 0,58 1.2 1.2 2,4 2,4 3.6 3.6 4.8 4.8

Nevertheless, if a higher degree of disinfection is required, it will be useful to bear


in mind several consequences which can be outlined as follows :

1. To obtain 9O% inactivation (1-log inactivation) of Giardia cysts, one CSTR


can be sufficient even if plug flow is in any case the best solution. But a
single CSTR can never provide a 3- or 4-log inactivation as EPA requires.
The theoretical contact time is very important, and it tends to infinity when
3-logs inactivation is overpassed.

2. To obtain 99% inactivation (2-logs inactivation) of Giardia cysts, a reactor


which has a hydraulic behavior of at least 3 CSTR in series is necessary.

3. To obtain 99.9% (3-logs) inactivation, a reactor which has the hydraulic


behavior of at least 5 CSTRs is necessary; this means a contactor with at least
two compartments, each of them having the behavior of 2-3 CSTRs in series.

4. To obtain 99.99% (4-logs) inactivation, a reactor representing more than 6


CSTRs in series is necessary (at least 8).
GIARDIA CYST INACTIVATION - KINETICS AND "CT" APPROACH 459

5. When passing from 1-log inactivation to 2-logs inactivation, the contact time
is multiplied by 2; when passing from 2-logs to 3-logs inactivation, the contact
time factor is 1.5; and, finally, in order to pass from 3-logs to 4-logs inactiva-
tion, the contact time should be multiplied by 1.33.

6. This kind of table can be obtained for other temperatures (from 5°C to
25 °C) and other concentrations of ozone (from 0.1 to 0.4 mg/L). One can
notice that the above conclusions concerning the inactivation requirements
remain valid in each of these cases.

It is now possible to try to formulate an answer to the question why the "CT"
concept chooses the value of T corresponding to F = 0.1. In Tables 9 and 10, the
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values of contact time calculated with F = 0.05, F = 0.1, and F = 0.2 are
represented. If a comparison is made between these values and that of the true
contact time (given by the kinetics), it can be noticed that the T 5 values approach
the best the T c values. This means that choosing the T 5 rather than T10 value to
determine the contact time will introduce a smaller error compared to the T c
value. Taking T 5 for the disinfection criterion will signify that 95% of the water
passing through the contactor will receive at least 99% inactivation (if 2-log
inactivation is applied to the system), and only 5% of the water will receive less
than 99% inactivation.

For proper transfer efficiency of ozone to water, ozone-containing systems are


designed to provide efficient mixing of water and applied gas in each segment of
the contactors. As a result, single chambers in ozone contacting systems do not
operate under plug flow conditions. However, if several individual contact
chambers are manifolded together in series, then the overall flow of water
through the multiplicity of ozonation chambers can at least approach plug flow
conditions to a considerable extent.

Summary And Conclusions

The Surface Water Treatment Rule (SWTR) uses the "CT" concept in order to
predict the inactivation efficiencies of Giardia cysts by disinfection. The exposure
time Tj., defined to assure that 9O% of the water entering the disinfection
chamber stays at least T10 minutes, depends on chamber hydraulics. On the other
hand, it is possible to predict the inactivation rate in a disinfection chamber by
integrating the inactivation kinetics and the hydraulic characteristics of the
chamber into a mathematical model. In this study these two approaches have
been compared.

The determination of contact time using the kinetics-and-hydraulics model should


be applied when high inactivation efficiency is required (3- or 4-logs) and the
hydraulic behavior of the reactor is close to that of a CSTR. The difference in
contact time values obtained by the two approaches is very significant in these
cases, and that is why the use of the "CT" approach is not correct and is not
recommended.
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6
Tab. 9. VALUES OF CONTACT TIME (min) C-0.1 mg/1 T-10' C ON
O

VI

s?

Inactlvatlon 90% 99% 99,90% 99,99%


model Tc Tff T'fo J:o Tc T5 T)0 Tc T.5 T» T«, Tc Tr, JiO

1 CSTR 19 96 48 21,8 206 190 95 43,2 2081 286 143 65 20831 386 193 88

3CSTR 7,2 23 13,3 10,2 22,8 45,2 26,4 20 56,3 68,1 39,7 30,4 128,4 92 53,6 41

4 CSTR 6,5 15 11.2 8,3 18 29,7 22,1 16 38,5 44,7 33 24,6 75 60,3 45 33

5 CSTR 6,1 11.7 10 7,4 15,8 23,2 20 14,6 31 34,9 29,8 22 55,2 47,1 40,2 30

T Q - real contact time obtained by the kinetics equation, min


T 5 - contact time obtained from the "F" curve ( F=0,05 ), min
T-|Q - contact time obtained from the "F" curve ( F=0,10), min
T20 - contact time obtained from the "F" curve ( F=0,20 ), min
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Tab. 10. VALUES OF CONTACT TIME (mln) C=0.4 mg/l T=10° C

52
i
Inadlvatlon 90% 99% 99,90% 99,99%
model Tc T5 T,o Tro Tc T5 T« T20 Tc T5 T10 T,, Tc Ts TV. Tin

1 CSTR 6,7 24 12 5,5 51,6 47,6 23,8 10,8 520,3 71,6 35,8 16,3 5208 96,6 48,3 21,9 O
•z
3 CSTR 1,8 5.7 3,3 2,6 5,7 11,3 6,6 5,1 14,1 17 10 7,6 32,1 23 13,4 10.3

o
4 CSTR 1,6 3,8 2,8 2,1 4,5 7.4 5.5 9.6 11.2 8.3 6,2 18,8 15,1 11,2 8.3

a
5 CSTR 1,5 2,9 2,5 1,8 4 5,8 5 3,7 7,8 8,7 7,5 5,5 13,8 11,8 10,1 7.4

TQ - real contact time obtained by the kinetics equation, min


Tg - contact time obtained from the "F" curve ( F=0,05 ), min o
T-jQ - contact time obtained from the "F" curve ( F=0,10 ), min
T20 - contact time obtained from the "F" curve ( F=0,20 ), min
462 M. Roustan et al.

When the contactor behavior approaches plug flow, for any inactivation efficiency,
the contact time can be determined by the "CT" method as well as by the
kinetics-and-hydraulics model. In the case of an ideal plug flow reactor, the
contact time obtained by the two approaches is the same.

The "CT" evaluation needs to be appropriate for ozone contactors in order to


avoid high ozone dosages and oversizing.

References
1. M. ROUSTAN; A. LINE; J.P. DUGUET; J. MALLEVIALLE; O. WABLE,
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"Practical Design of a New Ozone Contactor: The Deep U tube", in Proc.


European Ozone Congress, Belgrade, Yugoslavia (Paris, France: Intl. Ozone
Assoc, 1990), pp. 480-490.
2. R.G. RICE, 'The Safe Drinking Water Act Amendments of 1986: Their
Impacts on the Use of Ozone for Drinking Water Treatment in the United
States", in Proc. European Ozone Congress, Belgrade, Yugoslavia (Paris, France:
Intl. Ozone Assoc, 1990), pp. 181-196.
3. G.B. WICKRAMANAYAKE; O.J. SPROUL, "Ozone Concentration and
Temperature Effects on Disinfection Kinetics", Ozone: Science & Engineer-
ing 10(2):123-134 (1988).
4. O. LEVENSPIEL, Chemical Reaction Engineering, Second Edition (New York,
NY: John Wiley & Sons, Inc., 1972).
5. U.S. ENVIRONMENTAL PROTECTION AGENCY, Guidance Manual for
Compliance With the Filtration and Disinfection Requirements for Public Water
Systems Using Surface Water Sources (Washington, DC: U.S. EPA, Office of
Drinking Water, 1989).

Key Words

Ozone, Ozone Contacting, Disinfection, Contactor Hydrodynamics, Kinetics of


Ozone Disinfection, "CT" Values, Giardia Cyst Inactivation, Virus Inactivation

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