Water Research 36 (2002) 1043–1055

Wastewater disinfection by ozone: main parameters for

process design
Pei Xua, Marie-Laure Janexb, Philippe Savoyeb, Arnaud Cockxc,
Valentina Lazarovab,*
a
Laboratoire Hydrosciences, MSE, UMR no. 5569, Universite! Montpellier II, 34095 Montpellier cedex 5, France
b
Ondeo Services-CIRSEE, 38 Rue du President
! Wilson, 78230 Le Pecq, France
c
Laboratoire GPI, INSA, 135 avenue de Rangueil, 31077 Toulouse cedex 4, France
Received 1 March 2000; accepted 30 May 2001

Abstract

Wastewater disinfection by ozone was investigated at pilot scale on different wastewater effluents. Variations in
operating conditions showed that a very low hydraulic retention time (2 min) was sufficient for efficient fecal coliform
inactivation, provided a sufficient ozone dose was transferred to the effluent. Therefore, the transferred ozone dose
appeared to be the critical parameter for the design of wastewater disinfection. As a consequence, the ‘‘Ct’’ approach
commonly applied in drinking water treatment should not be used for wastewater ozonation. Design parameters of
ozonation were proposed for two types of regulations, and for effluents of different qualities. It was demonstrated that
only with an efficient filtration step one can meet stringent standards such as the California Title 22 criteria. In all cases,
viruses were totally inactivated; consequently, viruses do not constitute a limiting factor in wastewater disinfection by
ozone.
The standard drinking water model failed to match the experimental data obtained on real wastewater effluents.
A modified approach was successfully developed, based on the simultaneous consumption of ozone by the
microorganisms and the organic matrix. r 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Wastewater disinfection; Ozone; Process design; Water quality; Wastewater reuse; Disinfection modelling

1. Introduction reliability of wastewater disinfection, which is the most

Wastewater reuse has become an attractive option for
protecting the environment and extending available
water resources. In the last few years, there has been a
significant diversification of water reuse practices, such
as green space and crop irrigation, recreational im-
poundment, various urban uses including toilet flushing,
industrial applications and water supply augmentation
through groundwater or reservoir recharge [1,2]. The
safe operation of water reuse systems depends on the
*Corresponding author. Tel.: +33-134-802-251; fax: +33-
130-536-207.
E-mail address: valentina.lazarova@lyonnaise-des-eaux.fr
(V. Lazarova).
important treatment process for public health protec-
tion. The health-related microbiological regulations [3]
and the more recent impetus of producing virus-free
effluents [4] require the development of highly effective
advanced disinfection processes. Chlorination is still the
most widely used means to inactivate pathogenic
microorganisms in water and wastewater, but alterna-
tive technologies have to be evaluated because of
increasing concern over undesirable byproducts after
chlorination and its inefficiency in eliminating some
epidemic microorganisms at low chlorine doses [5,6].
Ozone has been proved to be one of the most effective
disinfectants and is widely used to inactivate pathogens
in drinking water, especially in Europe [7,8]. Design
engineers in the US began to evaluate ozone for

0043-1354/02/$ -see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 3 - 1 3 5 4 ( 0 1 ) 0 0 2 9 8 - 6
1044 P. Xu et al. / Water Research 36 (2002) 1043–1055
wastewater disinfection in the early 1970s. However,
because of operational and maintenance problems that
appeared in the first generation of facilities, it has been
considered to be a less attractive alternative to chlorine
than UV disinfection. Also, many researchers initially
sought to achieve a measurable level of dissolved ozone
residual in treated wastewater, which resulted in high
ozone dosages that were not economically feasible [9].
Earlier studies pointed out the need for a thorough
investigation of wastewater ozone treatment in order to
predict disinfection performance and design the disin-
fection system for wastewater disinfection [10–12].
The present study investigates the main factors related
to ozone disinfection performance, for the purpose of
facilitating its design and application to wastewater
disinfection.
2. Materials and methods
Experiments were performed in a continuous-flow
pilot plant with different types of effluents to evaluate
Fig. 1. Schematic diagram of the continuous-flow ozone pilot plant.
ozone disinfection performance on different target
microorganisms.
2.1. Experimental set-up: continuous-flow ozone pilot
plant
Ozonation tests were conducted in two different pilots
designed as bubble diffuser columns (Fig. 1), which were
operated in continuous counter-current mode. Ozone
between 2% and 6% was generated from oxygen (95–
98% purity), with generators provided by Ozonia. The
specifications of the ozone generators and contactors
used and the operating conditions are given in Table 1.
Tracer test studies were performed by impulse
injections of sodium chloride in the different operating
conditions on both pilots. This made it possible to
characterize the pilots as a series of two to five CSTRs.
Salt recovery showed that dead zones were between 5%
and 12% for the smaller hydraulic retention times
(HRT), and up to 25–30% for the highest HRT (10 min
in pilot 1, and 15 min in pilot 2). This was taken into
 P. Xu et al. / Water Research 36 (2002) 1043–1055 1045

Table 1
Characteristics of the ozone pilots and operating conditions used in the study

Parameter Pilot 1 Pilot 2

(Evry, France/Washington, UK) (Indianapolis, USA)

Column height, m 2.6 3.6

Column diameter, m 0.15 0.30
Porous plate porosity, mm 100 50
Hydraulic retention time, min 2–10 3–15
Number of CSTRs in seriesa 2–5 2
Applied ozone dose, mg L1 3–16/4–50 1–35
Transferred ozone dose, mg L1 2–13/4–30 0.5–12
a
Obtained by tracer tests in the different operating conditions.

account to calculate real contact times when data were an infinite rate constant
expressed as a function of ‘‘Ct’’. d½O3 
The ozone concentrations in the influent gas and off- ¼ KL að½O3  *  ½O3 Þ  kD ½O3  if TOD > X;
dt
gas were measured by UV absorbance monitors.
Residual ozone concentration in water was analysed d½O3 
by the indigo carmine method of [13], using HACH DR/ ½O3  ¼ 0 and ¼0 if TODoX; ð2Þ
dt
2000 spectrophotometer. The mass transfer efficiency in
the columns was found to be consistently 55% and 30– where KL a is the mass transfer coefficient; [O3]* is the
50%, respectively, in the pilots 1 and 2. In order to equilibrium (maximum) concentration of dissolved
compare the data, the transferred ozone dose (TOD) ozone, [O3], corresponding to Henry’s law; kD is the
was used as a descriptive parameter throughout the first order decay constant, in min1. TOD is the
study. It is defined as follows: transferred ozone dose calculated by
Z t
TOD ¼ Qgas =Qliq ð½O3 g in  ½O3 g out Þ; ð1Þ TOD ¼ KL að½O3  *  ½O3 Þ dt: ð3Þ
0

where Qgas and Qliq are gas and water flow rates,
respectively, [O3]g in is the ozone concentration in the
feed gas to the column, [O3]g out is the ozone concentra-
tion in the off-gas leaving the column. For a given set of
operating conditions, a time interval of three to four
times the mean hydraulic retention time was allowed to
reach steady state and take samples. In order to study
the effect of post-contact without additional ozone
introduction, water samples were taken from the outlet
of the column and were kept in a brown bottle without
light or air, to be analysed after a controlled contact
time.
2.2. Determination of ozone demand
The immediate ozone demand of the effluents, X; was
evaluated from the plots of the ozone residual vs. the
transferred ozone dose during disinfection tests, accord-
ing to the method proposed by Roustan et al. [14]. X
represents the minimum dose to be transferred to get
measurable ozone residual in the water. Mathematically,
the concept is represented by the following equations,
where the ‘‘instantaneous’’ demand would correspond to
Eq. (2) can easily be solved in an open, completely mixed
reactor (CSTR with a contact time t) to estimate the
ozone concentration
TOD  X
½O3  ¼ : ð4Þ
1 þ kD t
2.3. Wastewater characterisation
Effluents from three different wastewater treatment
plants (WWTP) were used for the studyFtwo second-
ary effluents and one tertiary effluent. The secondary
treatment trains in Evry, France (48,000 m3 d1) and
Washington, UK (90,000 m3 d1) are similar: pretreat-
ment, primary clarification, activated sludge (extended
aeration and high rate activated sludge, respectively),
secondary clarification and discharge. The tertiary
treatment train in Indianapolis, USA (300,000 m3 d1)
consists of dual media filtration and chlorination after
primary clarification, and coupled bio-roughing and
activated sludge nitrification facilities. The effluent for
pilot testing was taken after the tertiary filtration. The
main characteristics of the effluents during the tests are
given in Table 2.
1046 P. Xu et al. / Water Research 36 (2002) 1043–1055

Table 2
Wastewater characteristics, average (min–max)

Parameter Tertiary effluent Secondary effluent

Indianapolis (USA) Evry (France) Washington (UK)

1
Suspended solids (mg L ) 2.3 (o1–4) 5 (3–6) 18 (7–33)
COD, (mg O2 L1) 30 (24–38) 36 (26–56) 71 (41–150)
TOC (mg L1) 8 (5.5–10.2) o10 (o10–14) 26 (o11–30)
UV 254 abs (m1) 15.5 (12.5–20.8) 22.2 (17.4–20.8) 34.9 (26.0–50.9)
pH 7 (6.9–7.2) 7.3 (7.3–7.4) 7.5 (7.4–8.0)
Fecal coliforms (log CFU per 100 mL) F 3.6–4.5 4.3–6.5
E. coli (log CFU per 100 mL) 2.7–4.3 F F
Clostridium (log CFU per 100 mL) F 3.0–4.5 3.6–5.5

Table 3
Analytical methods for microbiological parameters

Parameters Analytical methods

E. coli (Indianapolis/Evry) Standard method 9222 O-M/Enterolert, Idexx (CIRSEE)

Fecal coliforms (Indianapolis/Washington) Standard method 9222 D-M/membrane filtration: incubation on 0.45 mm membrane
lauryl sulphate Broth for 4 h at 371C then 14 h at 441C. Enumeration of presumptive
fecal coliforms and confirmation by subculture into lactose peptone water at 371C in
conjunction with an oxidase test
Enterococci Membrane filtration: incubation on Slanetz and Bartley Agar for 4 h at 371C
followed by 44 h at 441C. Count all maroon colonies, confirmation on bile aesculin
azide agar
Clostridium Membrane filtration: heat-treat the sample at 751C for 10 min. Serially dilute and
vacuum filter appropriate dilutions/volumes through 0.45 mm membrane. Incubate
on Perfringens OPSP medium anaerobically at 371C for 48 h. Count all black
colonies and confirm in crossley milk
Enterovirus Suspended cell plaque assay: adsorption onto a cellulose nitrate membrane at pH 3.5;
elution by a positively charged protein solution; flocculation of the protein solution
and centrifugation; virus numeration by tissue culture assay (recovery quoted>20%)
F-specific RNA bacteriophages Incubation with a host strain: direct plating using a semi-solid overlay technique,
with Salmonella typhimurium WG49 as host bacterium (MS2 bacteriophage used as
positive control)
Salmonellae Filter appropriate volumes of sample through a 0.45 mm filter (using filter-aid if
turbid). Pre-enrich the filter in buffered peptone water for 24 h at 371C. Enrich a
0.1 ml portion of the culture in RVS broth for 48 h at 411C subculturing onto XLD
Agar and Brilliant Green Agar after 24 and 48 h. Presumptive Salmonellae are
confirmed serologically and biochemically

Fecal Coliforms and E. coli were chosen as standard
fecal indicators in the study, because they are usually
regulated for wastewater discharge or reuse. Other
microorganisms were also studied in the case of the
Washington effluent: enterococci Clostridium (as surro-
gates for more resistant organisms), Salmonellae, en-
teroviruses and F-specific bacteriophages (considered a
good model for virus disinfection [15]). The microbio-
logical methods used were based on the French and UK
Industry Standard Methods [16] with additional dilution
of the samples to appropriate levels. The analytical
methods are detailed in Table 3.
A number of physico-chemical parameters were
monitored on the effluents before and after ozonation
using Standard methods for pH, TOC, Turbidity, SS,
total and filtered COD, TOC, BOD5, UV 254 abs. (total
and after filtration), N–NO2, alkalinity, Mictotox tests
for toxicity and particle size distribution. To investigate
the effect of ozonation on colour abatement, absorbance
at 400 nm was used to characterise apparent colour.
Water appears to be coloured when dissolved matter
absorbs visible light or when suspended particles scatter
light (Rayleigh scattering). Finally, to stop the effect of
ozone residual on microorganism concentration after
 P. Xu et al. / Water Research 36 (2002) 1043–1055 1047

sampling, 4% (wt/vol) sodium thiosulfate was added to
the treated effluent samples.
To investigate the influence of particles on disinfection
performances, additional tests were run with the Evry
effluent after filtration (75 mm Arkal prefilter, followed
by a 10 mm canvas filter), to lower the suspended solids
concentration below 2 mg L1.
3. Results and discussion
3.1. Inactivation of fecal coliforms: impact of
operating conditions and wastewater quality
3.1.1. Influence of wastewater quality on ozone demand
Fig. 2 illustrates the determination of ozone demand
in the Washington secondary effluent for different values
of the hydraulic retention time. The measured values of
7.4–9.6 mg L1 are significantly higher than those in the
other two effluents, as expected from the water quality
data (see Table 2). The ozone demand of the Evry
secondary effluent (extended aeration with nitrification)
of 3.1–4.2 mg L1 is similar to the values measured in the
Indianapolis tertiary effluent of 2.5–5.3 mg L1. These
results are in agreement with an earlier study performed
on other effluents, which showed organic content to be a
much more influential parameter than suspended solids
on the ozone demand [12]. These values are used
hereafter when discussing the disinfection performances.
3.1.2. Influence of operating conditions on coliform
inactivation
Fig. 3 summarises the results from all the experiments,
where the residual concentration of bacteria after

Fig. 2. Determination of the immediate ozone demand according to the classical approach used for drinking water (effluent from
Washington, UK).

Fig. 3. Performances of ozone for FC inactivation on three different effluents: comparison of concentration level after ozonation with
reuse standards.
1048 P. Xu et al. / Water Research 36 (2002) 1043–1055
ozonation is plotted as a function of the transferred
ozone dose (TOD). One important observation is that a
significant 1–3 log inactivation is already reached when
TOD approximates the immediate ozone demand, i.e.
with no measurable residual of ozone in solution. This is
in agreement with earlier data on wastewater ozonation
[12]. More precisely, the higher the immediate ozone
demand, the higher the inactivation level reached at that
dose. This phenomenon can be explained by the fact that
bacteria themselves participate in the immediate ozone
demand, because of their high kinetic rate with ozone.
One important consequence from these results is that
design and control of ozonation for fecal coliform
disinfection in wastewater should not be based on the
standard parameter of residual ozone or ‘‘Ct’’ factor. In
agreement with this, Rakness et al. [10] reported that
direct measurement of ozone residual within the full-
scale contactors at Indianapolis had been unsuccessful
although good disinfection had occurred. The ‘‘Ct’’
approach is applied to drinking water because more
resistant microorganisms like Giardia are targeted.
Data from Fig. 3 show that the hydraulic retention
time (HRT) has no impact on the performances of fecal
coliform (FC) or E. coli disinfectionFfor a given TOD,
a 2 min HRT provides the same inactivation as 10 min
HRT. These results have major consequence for the
design of ozone wastewater disinfection, demonstrating
that mass transfer is the critical step that has to be
optimised, and that no long-contact-time chamber is
necessary.
Fig. 4 illustrates this statement, showing the distribu-
tion of ozone residual and FC inactivation along the
ozonation column and after 2, 4 and 6 min additional
Fig. 4. FC inactivation and residual ozone distribution vs. contact time in and after the ozone column (Washington secondary effluent,
HRT 4 min, TOD 13.1 mg L1).
contact in the post-contactor chamber. Residual ozone
decreased significantly in the post-contactor after 2 min
and no significant increase in FC inactivation is
observed. The quick decay of ozone may be explained
by the wastewater matrix-consuming ozone; therefore,
no further inactivation can be expected from a post-
contactor without additional ozone injection. As a
consequence, no credit of additional inactivation can
be attributed to a storage reservoir or outfall that would
be used for discharge of ozonated wastewater.
3.1.3. Effect of wastewater quality on ozone
disinfection performances
Despite similar values of immediate ozone demand
and not very different initial concentrations of bacteria,
the secondary and tertiary effluents of Evry and
Indianapolis display different inactivation performances
(see Fig. 3). It appears that only the tertiary effluent is
able to meet stringent standards for almost total bacteria
inactivation like the Californian Title 22 criteria. This
result led to a more in-depth investigation of the
influence of particles on disinfection.
Comparative tests were performed with the effluent
from Evry, and with the same effluent after a filtration
step. These tests were performed simultaneously in order
to minimise any fluctuation in water quality or operating
conditions. The ozone demand of the effluent was found
to be exactly the same. The effect of filtration on
disinfection is shown in Fig. 5: an additional 1 log
inactivation was obtained by filtration. It must be
stressed that for a given bacteria concentration (log N0),
a lower level of contamination was obtained after
filtration with the same ozone dose. This conclusion
 P. Xu et al. / Water Research 36 (2002) 1043–1055
Fig. 5. Impact of a 10 mm pre-filtration on the inactivation of total coliforms by ozone (secondary effluent in Evry, France).
explains the higher inactivation level obtained with the
tertiary effluent from Indianapolis, with its very low
suspended solids content.
3.2. Ozone disinfection of other microorganisms
In order to evaluate the disinfection efficiency of
ozone on other microorganisms, fecal streptococci (FS),
Clostridium, Salmonellae, Enterovirus, and F+-specific
bacteriophages were chosen as target microorganisms
for additional tests with the Washington secondary
effluent. The inactivation efficiencies are presented in
Table 4. It should be noted that the initial concentration
of microorganisms limited the maximum inactivation
values that could be reached. The resistance of fecal
coliforms and enterococci to ozonation was similar, in
agreement with previous results [17,18]. It is important
to stress also that a relatively low ozone dose of
8.6 mg L1 totally inactivates Salmonellae.
A higher efficiency of ozonation was observed for
virus inactivation: a transferred dose of 4.8 mg L1 with
4 min HRT was enough for total inactivation of
enteroviruses (>2.9 log inactivation). Total inactivation
of F+ coliphages (>2.2 log inactivation) was reached
with a slightly higher transferred dose of 8.6 mg L1.
The strong virucidal power of ozone for wastewater
disinfection confirms its well-known performance in
drinking water [7,18]. Indigenous enteric viruses isolated
from wastewater effluents have been shown to be much
more resistant [18]. In comparison, coliphages have been
found to be very sensitive to ozone, which puts some
doubt on the validity of these coliphages as surrogates
for enteric viruses [19,20].
This study shows that the ozone dose required to
satisfy WHO regulations (1000 FC per 100 mL) also
provides total inactivation of indigenous enteric viruses.
This indicates that ozone would be highly recommended
for the production of virus free water, required in several
1049
countries for landscape (Australia, 1 pfu/50 L) or agri-
cultural irrigation (Arisona and Hawaii, USA, 1 pfu/
40 L).
Compared to all other microorganisms, the higher
resistance of Clostridium was confirmed by the experi-
mental data. A thorough investigation was made with
the effluents from Evry and Washington with that
indicator (Fig. 6). With a TOD approximately equal to
the immediate ozone demand of the effluents (3–
5 mg L1 for Evry and 8–10 mg L1 for Washington),
less than 0.5 log inactivation of Clostridium was
achieved. The maximum inactivation level was less than
2 log for high TOD of 33 mg L1 (HRT 9.6 min,
Washington secondary effluent).
3.3. Impact of ozonation on effluent water quality
Due to the high oxidative potential of ozone,
ozonation has a beneficial effect on effluent quality,
which argues in favour of its application for wastewater
reuse (Table 5). The most significant effect of ozone was
on UV-254 absorbance and colour (Figs. 7a and b).
With an increase in transferred ozone dose from 2 to
13 mg L1 at HRT 4 min, the variation of UV absor-
bance in the Evry secondary effluent increased from
28% to 55%. These results indicate that the ozone reacts
and oxidises the organic matter, in particular, the
compounds having double bonds and/or an aromatic
structure that determine the value of the absorbance at
254 nm. The UV absorbance abatement was higher in
the Evry secondary effluent than in Washington,
indicating the presence of refractory contaminants.
Finally, no significant difference was observed between
different contact times in the reactor (not shown),
revealing the fast kinetics of the reaction between ozone
and unsaturated and aromatic compounds. The critical
factor for water quality improvement is also the ozone
dose transferred into the water.
1050 P. Xu et al. / Water Research 36 (2002) 1043–1055

Total BOD5 increased up to 20% after ozonation of

F-coliphage (/mL)

1.68
>2.16
>2.09
the highly polluted secondary effluent in Washington,

Red
UK. This is typical with ozone, which can oxidise
recalcitrant compounds and thereby increase effluent
N

2
0
0
biodegradability. The total COD was not significantly
influenced by ozonation, while an increase of dissolved
96
144
122
N0

COD was observed. The difference between total and

dissolved COD behaviours could be related to the global
Enterovirus (pfu/10L)

1.66
>2.89

>2.81
>2.82
>2.89
>2.89
decrease of turbidity observed during the tests (Fig. 7-
Red

c)Fsome particles and high weight organic compounds

would be destroyed by ozone and converted into
dissolved compounds.
12
0

0
0
0
0
N

Toxicity was detected neither in the untreated

secondary effluent nor in the ozonated effluents. These
775
544
650
654
774
774
N0

results are in compliance with previous studies on urban

wastewater disinfection by ozone [17]. It is important to
Abs
Abs
Abs
Abs
Abs
Salmonella

stress that the presence of toxicity after ozonation

N

reported in the literature is usually related to the

Prst
Prst
Prst
Prst
Prst

presence of industrial wastewater [21–24].

F
N0

3.4. Design of wastewater ozonation for given regulations

0.88
1.64
2.50
2.26
3.56
3.33
Red
Enterococci (/100 mL)
Comparison of ozone disinfection on different microorganisms in the secondary effluent in Washington, UKa

Ozone disinfection results were compared for two

7100
980
173
400
14
16

different water reuse standards: (1) WHO stringent

N

guidelines for irrigation, fecal coliformso1000 cfu per

100 mL, and (2) Californian Title 22 standards, total
log N0

4.73
4.63
4.74
4.86
4.71
4.53

coliformso2.2 cfu per 100 mL (see Fig. 3). The TOD

required to meet WHO guidelines are 2, 4 and
15 mg L1, respectively, for the tertiary affluent and the
0.31
0.21
1.16
1.72
Red
Clostridium (/100 mL)

two secondary effluents in Evry and Washington for an

F
0

HRT of 2 min and an additional beneficial effect of 30%

21000
6200
4800
3100

2000
550

reduction in UV absorbance. Compliance with the

stringent Title 22 criteria of virtually total removal of
N

fecal coliforms can be reached only after tertiary

log N0

filtration in the Indianapolis effluent and with a TOD

3.56
3.67
3.81
4.53
4.46
4.46

of 8 mg L1 for 2 min HRT. A very low suspended solids

concentration (o5 mg L1) emerges as the most im-
HRT min TOD (mg L1) Fecal coliform (Cfu per 100 mL)

portant design requirement to meet very stringent

Note: RedFlogðN0 =NÞ; PrstFpresent; AbsFabsent.
0.34
1.82
2.48
2.52
4.42
4.06
Red

disinfection requirements.
In both scenarios, total inactivation of viruses is
achieved, which may be important if viruses are also
included in regulations.
4600
1320
300
840
14
14
N

3.5. Modelling approach of wastewater disinfection

by ozone
log N0

5.00
4.94
4.95
5.45
5.92
5.20

Disinfection is standardly described, for drinking

water, by the Chick–Watson model:
d½N 
¼ kN ½N½O3 : ð5Þ
dt
15.2
11.0
24.8
29.5
4.8
8.6

In the case of a CSTR, Eq. (5) enables the evaluation of

the number of microorganisms, N:
Table 4

½N 1
¼ ; ð6Þ
a
9.6
9.6
9.6

½N0  1 þ kN ½O3 t
4
4
4
 P. Xu et al. / Water Research 36 (2002) 1043–1055 1051

Fig. 6. Performances of ozone for Clostridium inactivation. (secondary effluents of Washington, UK and Evry, France).

Table 5
Impact of ozonation on water quality in Washington, UKa

Parameters HRT 4.0 min HRT 2.0 min HRT 9.6 min HRT 4.0 min
TOD 9.2 mg L1 TOD 12.3 mg L1 TOD 15 mg L1 TOD 21.1 mg L1

C0 9 24 17 10
TBOD C 8 30 21 12
(mg L1) ðC  C0 Þ=C0 11% +25% +24% +20%
C0 73 94 93 70
TCOD C 66 92 94 69
(mg L1) ðC  C0 Þ=C0 10% 2% +1% 1%
C0 42 43 47 38
DCOD C 42 51 63 47
(mg L1) ðC  C0 Þ=C0 0% +19% +34% +24%
Total C0 0.44 0.48 0.51 0.43
UV Abs C 0.36 0.4 0.39 0.27
(Cm1) ðC  C0 Þ=C0 20% 17% 24% 38%
Dissolved C0 0.22 0.23 0.23 0.22
UV Abs C 0.17 0.17 0.17 0.12
(Cm1) ðC  C0 Þ=C0 25% 24% 27% 44%
a
C0 is the initial concentration of secondary effluent; C is the concentration of ozonated effluent.

where N is the density of viable microorganisms (N0 at kinetics, characterised by coefficient rates kX and kY
t ¼ 0), t is the hydraulic retention time in the reactor, [25]:
and kN is the inactivation rate constant.
In fact, the use of the Chick–Watson model implies d½O3 
¼ KL að½O3  *  ½O3 Þ  kX ½X½O3   kY ½Y½O3 ;
the presence of ozone residual to achieve inactivation of dt
microorganisms; there would be no disinfection before ð7Þ
the ozone demand is met, i.e. for transferred ozone doses
lower than 8 mg L1, the immediate ozone demand of d½Y 
¼ kY ½Y½O3 ; ð8Þ
wastewater. dt
In order to account for the 1–3 log inactivation
observed without measurable residual in wastewater d½X 
¼ kX ½X½O3 : ð9Þ
ozonation, a modified approach was therefore devel- dt
oped, considering the consumption of ozone by the The comparison with the previous equations used for
organic matter as a combination of a rapid and a slow drinking water shows that we can obtain the same model
1052 P. Xu et al. / Water Research 36 (2002) 1043–1055
Fig. 7. Influence of ozonation on wastewater quality. (a) Total
and dissolved UV-254 absorbance removal vs TOD (4 min
HRT, secondary effluents of Washington, UK and Evry,
France), (b) colour removal vs TOD at different contact times
(Evry secondary effluent) and (c) turbidity change versus
transferred ozone dose (Washington secondary effluent).
by simplification if
kD ¼ kY ½Y;
kX ¼ N:
Eqs. (7–9) can easily be solved in an open completely
mixed reactor (CSTR with a contact time t) to estimate
ozone concentration and also concentrations of the
different species X and Y (rapidly consumed and the
slowly consumed organic matter):
DOT
½O3  ¼ ð10Þ
1 þ kX ½Xt þ kY ½Yt
½Xo 
½X ¼ ; ð11Þ
1 þ kX ½O3 t
½Yo 
½Y ¼ : ð12Þ
1 þ kY ½O3 t
The use of these equations should be interpreted as a
valid model for quantification but not necessarily as an
accurate representation of the more complex mass
transfer steps and heterogeneous reactions taking place
during the disinfection process. In particular, radical
mechanisms are ignored for simplification. Besides, in a
first step, hydraulic aspects are ignored in the inter-
pretation of the data and we assume that the bubble
column can be represented as a CSTR, which is close
enough to the experimental data. The focus is on the
kinetic modelling, which can be completed afterwards
with hydrodynamic information. The exact value of the
fitting parameters will then be slightly altered, but not
their order of magnitude. A very similar approach was
taken by Hunt and Marinas * [26] on the inactivation of
E. coli with ozone in synthetic waters.
This modified approach was applied to the experi-
mental data from Washington WWTP, with residual
ozone as a function of TOD. It led to the following
fitting parameters (Fig. 8):
kX ¼ 10 L mg1 min1 ;
kY ¼ 0:01 L mg1 min1 ;
½Xo  ¼ 8 mg L1 ;
½Yo  ¼ 60 mg L1 :
This represents a first improvement, but the major
difference between both models appears when consider-
ing the inactivation of fecal coliforms. For transferred
ozone doses lower than the fast ozone demand,
integrated exposure to ozone in terms of Ct is equal to
zero for the classical approach and reaches
0.40 mg min L1 with the modified model for a TOD
of 8 mg L1. When applying the Chick–Watson model
given by Eq. (5), this slight difference in the Ct makes it
possible to account for the inactivation of fecal coli-
forms during X organic matter consumption. Fig. 9
shows the strong impact of this low Ct in wastewater,
which inactivates 2 log of E. coli. The corresponding
inactivation rate constant kN is equal to
100 L mg1 min1 and the fitting curves are depicted in
Figs. 9a and b. Besides, the model properly accounts for
the fact that the contact time has no effect on
 P. Xu et al. / Water Research 36 (2002) 1043–1055 1053

Fig. 8. Modelling of the residual ozone with the modified approach developed for wastewater disinfection.

Fig. 9. Inactivation of E. coli with ozone for the classical (a) and modified (b) models applied to disinfection in wastewater effluent.

inactivation performances. Therefore, a significant im-
provement is observed when the apparent ozone
decomposition is represented as a mixed second order
rate expression depending on the fast ozone demand X
(Eq. (11)).
4. Conclusions
The experimental results obtained at pilot scale on
different wastewater effluents confirm the efficiency of
ozone for wastewater disinfection. Depending on the
quality of the effluent, a TOD of between 2 and
15 mg L1 was necessary to meet the WHO standard
for irrigation (1000 FC per 100 mL). Such a dose was
shown to provide total elimination of enteroviruses in
the worst quality secondary effluent, which can be a
major advantage of ozone for regulations that include
virus removal. In agreement with previous data,
bacteriophages were found very sensitive to ozone,
laying doubt on the pertinence of such microorganisms
as indicators for ozone treatment. By contrast, the
higher resistance of Clostridium confirms that they are
good candidates for resistant microorganism indicator.
Ozonation also provides a significant reduction of UV
absorbance and colour, which can be an advantage for
some reuse applications. More stringent regulations like
Title 22 require the implementation of an efficient
tertiary filtration step.
From an operational viewpoint, transfer of ozone
from the gas phase to the water was found to be the
critical step for fecal coliform inactivation with ozone,
because of the fast kinetics between ozone and coliform
bacteria. No difference in inactivation was found
1054 P. Xu et al. / Water Research 36 (2002) 1043–1055
between 2 and 10 min hydraulic retention time, for a
given ozone dose transferred to the effluent. As a
consequence, the ‘‘Ct’’ approach commonly applied in
drinking water treatment should not be used for the
ozonation of wastewater. The new approach to waste-
water ozone contactor design must be based on short
contact times and enhanced mass transfer. Further, no
credit of inactivation can be attributed to a storage
reservoir or outfall that would be used for wastewater
discharge after ozonation, because of high ozone decay
in an effluent matrix.
Finally, a kinetic model was developed in order to
account for the 1–3 log inactivation of bacteria that was
observed experimentally without a measurable concen-
tration of ozone in the bulk solution. In fact, a
combination of the classic Chick–Watson disinfection
model and the ‘‘instantaneous demand’’ model used in
drinking water was insufficient. The modified model was
based on the simultaneous consumption of ozone by the
microorganisms and by the organic matrix. The
apparent decomposition rate of dissolved ozone was
represented successfully by mixed second-order rate
equations.
Acknowledgements
The authors would like to thank Luc Burtin
(CIRSEE) for technical assistance, Ozonia for the
provision of an ozone generator, Evry and Washington
wastewater treatment plants staff for field assistance,
CIRSEE and Northumbian Water Group of Ondeo
Services for cooperation and lab analysis.
References
[1] Lazarova V. Role of water reuse in the integrated resources
management: costs, benefits and technological challenges
# de la r!eutilisation des eaux us!ees pour la gestion
(Role
int!egr!ee des ressources: couts,
# b!en!efices et d!efis technolo-
giques). Leau, Lindustrie, Les nuisances 1999;227:47–57.
[2] Lazarova V, Cirelli G, Jeffrey P, Salgot M, Icekson N,
Brissaud F. Enhancement of integrated water management
and water reuse in Europe and the Middle East. Water Sci
Technol 2000;42(1/2):193–202.
[3] Levine B, Lazarova V, Manem J, Suffet IH. Wastewater
reuse standards: goals, status and guidelines. WEF
beneficial reuse of water and biosolids Conference
Proceedings, Marbella, 6–9 April 1997; 13/59–13/71.
[4] USEPA Manual (1992). Guidelines for water reuse. EPA/
625/R-92/004.
[5] Tyrrell SA, Rippey SR, Watking WD. Inactivation of
bacterial and viral indicators in secondary sewage efflu-
ents, using chlorine and ozone. Water Res 1995;29(11):
2483–90.
[6] Lazarova V. Wastewater disinfection: assessment of the
available technologies for water reclamation. In: Goosen
MFA, Shayya WH, editors. Water management, purifica-
tion and conservation in arid climates, Water Conserva-
tion, vol. 3. Technomic p. 171–98.
[7] Langlais B, Reckhow D.A, Brink DR. Ozone in water
treatmentFapplication and engineering. Co-operative
Research Report. Lewis, 1991.
[8] Facile N, Barbeau B, Pr!evost M, Koudjonou B. Evaluat-
ing bacterial aerobic spores as a surrogate for Giardia and
Cryptosporidium inactivation by ozone. Water Res
2000;34(12):3238–46.
[9] Robson CM, Rice RG. Wastewater ozonation in the
USAFhistory and current statusF1989. Ozone Sci Eng
1991;13:23–40.
[10] Rakness KL, Corsaro KM, Hale G, Blank BD. Waste-
water disinfection with ozoneFprocess control and
operating results. Ozone Sci Eng 1993;15:497–514.
[11] Hunter GF, Rakness KL. Start-up and optimization of the
ozone disinfection process at the Sebago Lake water
treatment facility. Ozone Sci Eng 1997;19:255–72.
[12] Janex ML, Savoye P, Roustan M, Do-Quang Z, La#ın!e JM,
Lazarova V. Wastewater disinfection by ozone: influence
of water quality and kinetics modelling. Ozone Sci Eng
2000;22(2):113–22.
[13] Bader H, Hoigne J. Determination of ozone in water by
indigo methods: a submitted standard method. Ozone Sci
Eng 1982;4:169–76.
[14] Roustan M, Debellefontaine H, Do-Quang Z, Duguet JP.
Development of a method for the determination of ozone
demand of a water. Proceedings of IOA Congress, Kyoto,
1997. p. 589–94.
[15] Hall RM, Sobsey MD. Inactivation of hepatitis A virus
and MS2 by ozone and ozone-hydrogen peroxide in
buffered water. Water Sci Technol 1993;27(3–4):371–8.
[16] HMSO Publication (1994). The microbiology of water
1994FPart 1Fdrinking water. Report on public health
and medical subjects No. 71. Methods for the examination
of waters and associated materials.
[17] Mandra V, Lazarova V, Dumoutier N, Audic JM.
Comparative study of urban sewage disinfection by
peracetic acid, UV and ozone (Etude comparative de la
desinfection des eaux r!esiduaires urbains par l’acide
perac!etique, l’irradiation UV et l’ozone). Journ!ees Infor-
mation Eaux, Poitiers, 18–20 September, 1996.
[18] Hartemann PH, Block JC, Joret JC, Foliguet JM, Richard
Y. Virological study of drinking and wastewater disinfec-
tion by ozonation. Water Sci Technol 1983;15:145–54.
[19] Helmer RD, Finch GR. Use of MS2 coliphage as a
surrogate for enteric viruses in surface waters disinfected
with ozone. Ozone Sci Eng 1993;15:279–93.
[20] Harakeh MS, Butler M. Factors influencing the ozone
inactivation of enteric viruses in effluent. Ozone Sci Eng
1985;6:235–43.
[21] Langlais B, Legube B, Beuffle H, Dor!e M. Study of the
nature of the by-products formed and risks of toxicity
when disinfecting a secondary effluent with ozone. Water
Sci Technol 1992;25(12):135–43.
[22] Paraskeva P, Lambert SD, Graham NJD. Influence of
ozonation conditions on the treatability of secondary
effluents. Ozone Sci Eng 1998;20:133–50.
[23] Ito K, Jian W, Nishijima W, Base AU, Shoto E, Okada M.
Comparison of ozonation and AOPs combined with
 P. Xu et al. / Water Research 36 (2002) 1043–1055 1055

biodegradation for removal of THM precursors in
treated sewage effluents. Water Sci Technol 1998;
38(7):179–86.
[24] Monarca S, Feretti D, Collivignarelli C, Guzzella L,
Zerbini I, Bertanza G, Pedrazzani R. The influence
of different disinfectants on mutagenicity and toxicity
of urban wastewater. Water Res 2000;34(17):4261–9.
[25] Cockx A, Janex ML, Lazarova V. Development of ozona-
tion modelling for the disinfection of wastewater effluents.
Proceedings of the International Ozone Association
Conference, Wasser Berlin, 23–26 October 2000. p. 79–93.
[26] Hunt NK, Marinas* B. Inactivation of Escherichia coli with
ozone: chemical and inactivation kinetics. Water Res
1999;33(11):2633–41.