Wat. Res. Vol. 28, No. 10, pp.

2153-2164, 1994

Pergamon

0043-1354(94)E0019-3

Copyright 1994 Elsevier Science Ltd

Printed in Great Britain. All rights reserved
0043-1354/94 $7.00 + 0.00

A D V A N C E D OXIDATION OF ATRAZINE IN
WATER--I. OZONATION
FERNANDO J. BELTR,~,N* ~), JUAN F. GARCiA-ARAYA a n d BENITO ACEDO
Departamento de Ingenieria Quimica y Energ6tica, Universidad de Extremadura, 06071 Badajoz, Spain

(First received February 1993; accepted in revisedform January 1994)

Abstract--The ozonation of atrazine in water has been studied under different conditions of ozone partial
pressure, pH, temperature and presence of hydroxyl radical scavengers. The process mainly develops
through radical reactions, even at pH 2, probably due to the presence of traces of impurities in the starting
material. The rate constant of the direct reaction between ozone and atrazine at pH 2 has been determined
and expressed as a function of temperature. Thus, at 20C the rate constant was found to be 4.5 M - t s - t
the energy of activation being 18.8 kJ m o l - t . A model formed by mol balance equations of atrazine and
ozone, the latter in the liquid and gas phases, with the ozone decomposition rate based on the Staehelin
and Hoign6 mechanism allowed the determination of the concentrations of these species at different
experimental conditions. The aqueous solution of atrazine is characterized by a hydroxyl radical initiating
rate factor which accounts for other radical reactions not included in the basic ozone decomposition
mechanism. With this factor deviations between experimental and calculated concentrations of atrazine
are less than + 15% in most of the cases.

Key words--atrazine, advanced oxidation, ozone, ozonation, kinetics, water treatment

k~ = pseudo first order rate constant defined by equation

(14) (s - i )
k~ = rate constant of the hydroxyl ion catalysed decomposition reaction of ozone (1 tool- i s - ~)
k t = rate constant of reaction (38) (1 tool -I s -I)
ke = individual liquid phase mass transfer coefficient
(ms-')
ko~t,A = rate constant of the reaction between atrazine and
the hydroxyl radical (1 tool -i s - ~)
k~ = rate constant of the reaction between the intermediate i and the hydroxyl radical (1 tool- ~s - ~)
k~ = rate constant of the reaction between the scavenger
i and the hydroxyl radical (1 tool- 1s - l )
k z = apparent pseudo first order rate constant of the
ozonation of atrazine defined in equation (40) (s-i )
kt = rate constant of second order termination for
hydroxyl radicals (1 tool- 1s - l )
Posi = ozone partial pressure at the reactor inlet (Pa)
m = reaction order of ozone in its irreversible reaction
with species B (dimensionless)
n = reaction order of species B in its irreversible reaction
with ozone (dimensionless)
R = gas constant (J K - ~tool- ~)
T = temperature (K)
t = time (s)
t~ = time to reach the stationary concentration of ozone
(s)
Vo = gas volume accumulated in the reactor (1)
Vc = liquid volume in reactor (1)
v0 = gas volumetric flow rate (1 s - t )
z = stoichiometric ratio of the direct reaction between
atrazine and ozone (dimensionless)

NOMENCLATURE
CA = concentration of atrazine (tool 1-~ )
CAo = initial concentration of atrazine (mol 1- ~)
(;'As = concentration of atrazine defined in equation (15)
(moll a)
CB = concentration of species B (mol 1- z)
C~ = concentration of species I that initiates the formation of hydroxyl radicals (mol 1- J)
Con = concentration of hydroxyl radicals (mol 1-1)
Con~p = experimental concentration of hydroxyl radicals
calculated by equation (41) (tool 1-1)
Co~-= concentration of superoxide ion radical (tool 1-1 )
Cos = concentration of dissolved ozone (tool 1- ~)
C ~ = concentration of ozone at the gas-water interface
or solubility (tool I 1)
Co,g = concentration of ozone in the gas at the reactor
outlet (tool 1 ~)
Costa = average value of dissolved ozone concentration
(mol 1- J)
Cojs = stationary concentration of dissolved ozone
(mol I l)
Dos = diffusivity of dissolved ozone (m 2 s - i )
H = Henry constant (Pa I mol -t )
Ha = Hatta number defined in equation (28) (dimensionless)
Koa =overall mass transfer coefficient [mol (lgas) -~
Pa 1 s - l ]
Koa' = overall mass transfer coefficient (tool 1-i Pa-1 s - l )
k = rate constant of the irreversible reaction between
ozone and species B (1 tool- 1 s - 1)
kA = actual rate constant of the direct reaction between
unprotonated form of atrazine and ozone
(1 tool -I s - l )
k d = rate constant of the direct reaction between atrazine
and ozone at pH 2 (1 tool -j s -~)

Greek letters

*Author to whom correspondence should be addressed.

2153

= degree of protonation of atrazine (dimensionless)

fl = hydroxyl radical initiating rate factor (tool 1- ~s- ~),
defined by equation (42)
)'o3 = percentage of the elimination of atrazine due to its
direct reaction with ozone, defined in equation (39)
(dimensionless)

FERNANDOJ. BELTR./~Net al.

2154
INTRODUCTION

Atrazine is one of the most used herbicides worldwide

and constitutes a priority pollutant of the water
(Battaglia, 1989). Since atrazine has been found in
many water environments at very low concentrations
[although higher than its maximum contaminant level
(Croll, 1989)], oxidation is one of the best methods to
degrade it. In a previous paper (Beltrfin et al., 1993)
it was shown that the combination of ultraviolet
radiation and hydrogen peroxide lead to high degradation rates of atrazine. Accordingly, advanced oxidation processes can be a convenient way to oxidize
atrazine.
This work, divided in two parts, deals with the
oxidation of atrazine with ozone and u.v. radiation
(03 and u.v./O3), processes that like the combination
of u.v. radiation and hydrogen peroxide (Beltr~n
et al., 1993), generate hydroxyl radicals. In the first
part of this work, ozonation of atrazine is studied, the
major aims being the determination of the rate
constant of the direct reaction ozone-atrazine, the
comparison of the importance of direct and radical
ways of ozonation and the study of the oxidation
kinetics. In the second part, the u.v./O3 oxidation
results are presented (see subsequent paper, Beltr~n
et al., 1994).
The ozonation of atrazine in water has already
been treated by different authors to identify the main
by-products formed and establish molecular mechanisms. Chronologically, Erb et al. (1979) were the first
to study this process to report some data about the
degradation rate of the herbicide. Later, Legube et al.
(1987) evaluated the ozone demand of atrazine solutions at slightly acid pH, but the main objective of
their work was to identify secondary products. In
another work Adams et al. (1990) also studied the
ozonation of atrazine and derivative compounds, like
deethylatrazine, deisopropylatrazine and 2-chloro4,6-diamino-s-triazine to quote a few. Like Legube
et al., they proposed a molecular mechanism indicating the importance of contact time, p H and ozone
concentration on the rate of reactions. More recently,
Adams and Randtke (1992) reported additional data
about the ozonation by-products, highlighting the
differences in the nature of these intermediates when
carbonate ions are present.
As far as kinetics is concerned, Adams et al. (1990),
Yao and Haag (1991) and Xiong and Graham (1992)
have reported on values of the rate constant of the
direct reaction between ozone and atrazine at specific
conditions of temperature (20C) and pH. Table 1
lists their results. The lack of information about the
contribution of radical reactions and discrepancies in
the rate constant data made necessary further studies,
which were one of the objectives of this work.
EXPERIMENTAL SECTION AND ANALYSIS
The experimental set-up basically consisted of an ozonator (SLO Constrema) and a 850 cm 3 glass reactor described

Table I. Rate constants of the direct reaction between ozone and

atrazine reported in literature
kd
Scavenger
pH (M-Is ~) and concentration
Reference
2a
2.25 t-Butanol,0.01 M Xiongand Graham (1992)
7.5"
12.24 Carbonate,10-4M Xiongand Graham (1992)
4.1b
6
t-Butanol,0.01M Yao and Haag (1991)
5b
73c
-Adams et al. (1990)
7b
146
-Adams et al. (1990)
9b
617
-Adams et al. (1990)
7~
12Y
-Adams and Randtke (1992)
aBatch competitiveozonation with MCPA as reference compound.
bBatch ozonation. CReportedas total rate constant, dContinuous
ozonation.

in detail previously (Beltr~n et al., 1993). Ozone produced

in the ozonator from oxygen was fed into the reactor,
filled with 800 cm 3 aqueous buffered solution of atrazine,
through a porous plate (of 16 #m mean porosity) situated
at the bottom. The experimental conditions are given in
Table 2.
Atrazine was analysed by liquid chromatography as
described before (Beltr~in et al., 1993). Ozone both in
the liquid and in the gas phase, at the reactor inlet and
outlet, was measured colorimetrically (Bader and Hoignr,
1981) and iodometrically, respectively. In some experiments
the ozonation was carried out in the presence of
known amounts of t-butanol (pH2) or bicarbonate/carbonate ions (pH 7 and 12) that acted as scavengers of
hydroxyl radicals.
RESULTS AND DISCUSSION
First the influence of variables (see Table 2) on the
degradation rate of atrazine was studied. Both the
ozone partial pressure and pH exert a strong effect,
increasing the atrazine conversion with the increase
of each of these variables. Figure 1 shows, as an
example, the effect of pH. These results are, on one
hand, a logical consequence of the increase of the
ozone driving force by increasing the ozone partial
pressure and, on the other hand, of the higher
decomposition of ozone into radicals when pH increases. As shown in Fig. l(b), the concentration of
dissolved ozone increases with time, only for a few
minutes, until reaching a stationary value. At any
given time, this concentration decreases with the
increasing pH probably due to the more important
contributions of radical reactions at high pHs. In any
case the most noticeable fact, the presence of dissolved ozone, suggests that the ozonation of atrazine,
regardless of the mechanism (through direct or radical reactions), is a set of slow gas-liquid reactions. At
this point, however, it has to be pointed out that at

Table 2. Experimental conditions applied in this work

CAo(M)
4.2 10 5to 7.3x10 5
Po3i (Pa)
500 to 2000
T (C)
3, 10 and 20
pH
2, 7 and 12
Cs as t-butanol (M)
0 to 0.05
C~ as total bicarbonate (M)
0 to 0075
Gas flow rate (l h -t)
50
Ionic strength (M)
0.01

Ozone oxidation of atrazine

2155

1.0
10

I \a"
!~ \ \ ' \ \

~
o

OJ

-t,
-I t

s, ~'

\{

\,,

a\

\\
o x.

I l l i l
4
8

"~o ~

N
i
12

i
16

J
20

i
24

~)

-0

12

16

20

24

30

time, rain

time, m l n

(a)

(b)
o

e"

e" - - " ~ - - - - -- - - - - o" " ~

(o

o
o

20

24

30

time, m k l

(c)
Fig. 1. Influence of pH on the ozonation of atrazine. Variation of concentrations with time: (a) atrazine
as CA/CAo; (b) dissolved ozone; (c) ozone in the gas. Conditions: C) pH 2; [] pH 7; ~ pH 12.
Po3~= 1050Pa, CA0= 5 x l0 -5 M (average values).

pH 12 (see later) the very low concentration of dissolved ozone indicates a change in the kinetic regime
of absorption that becomes moderate (Charpentier,
1981).
A similar pattern to that shown in Fig. l(b) was
followed by the concentration of ozone in the exiting
gas [see Fig. l(c)]; in this case, however, the stationary
concentration of ozone is apparently independent of
pH.
Figure 2 shows the effect of inhibitors of hydroxyl
radicals on the degradation of atrazine. Two strong
inhibitors were used, t-butanol and bicarbonate/
carbonate ions in addition to phosphates to buffer
the aqueous solutions that are also weak scavengers
(Staehelin and Hoign6, 1982). The effect, as observed
from Fig. 2, was checked at three pH levels (2, 7 and
12). It is evident that atrazine is degraded through
radical reactions even at pH 2, so that the ozonation
of atrazine is mainly an advanced oxidation, although
at acid pH the contribution of its direct reaction with
ozone can be important as shown later.
Finally, the effect of temperature is shown in
Fig. 3. Here, results corresponding to two series of
ozonation reactions are plotted. In one series, the
ozonations were carried out at the same ozone partial

pressure whilst in the other the effect of this variable

on the ozone solubility was corrected and different
ozone partial pressures were applied. Thus, when the
ozone partial pressure was the same (about 1100 Pa)
there were no appreciable differences between the
values of the remaining concentration of atrazine
with temperature. Since the degradation rate of
atrazine is proportional to the rate constant, and
hence to temperature, one should expect, a priori, a
positive influence of this variable on the oxidation
rate of atrazine. However, as ozonation is a gas liquid
reaction, the oxidation rate also depends on the
ozone solubility which decreases with the increasing
temperature (Sotelo et al., 1989). Thus, both effects,
increase of the rate constant and decrease of the
ozone available for reaction, are opposed and the
final consequence is that temperature does not exert
any significance influence on the elimination of
atrazine, at least under the conditions applied in this
work (3-20C).
In the second series of ozonations, the ozone
partial pressure applied was corrected so that the
ozone solubility, and hence the ozone available for
reaction, was the same at different temperatures.
These experiments were also carried out in the

FERNANDOJ. BELTR~Net al.

2156
1.0

i" ..a

t-Butanol

pH2

\X "~ ~

COx 102, M
o=, 01

'~.,p~ "....=..
\

\\

"~

0.5

~"~t,

,'-..

,,..

,e, 5

,..

i
4

i
8

i i i , , , i t i ,
12
16
20
24
28

time, min
1.0
in
I'~
,,,

pH

~,%~
-\ ~'\q\\

*~

pH 12

Bicarbonate ion
C s, M

0.075

\ 'k2,
\

The results shown in the previous section indicate

that the ozonation of atrazine depending on the
experimental conditions is carried out through direct
reaction with ozone (i.e. at pH 2 and in the presence
of t-butanol) and via radicals (hydroxyl radicals)
a priori formed from the decomposition of ozone
(Staehelin and Hoignr, 1985). On the other hand
the presence of important amounts of dissolved
ozone (especially at pH < 12) suggests undoubtedly
that the chemical reactions develop in the bulk water
(Danckwerts, 1970; Charpentier, 1981; Beltrfin et al.,
1992). Under these circumstances and assuming
that the ozonation of atrazine follows the wellknown mechanism of Staehelin and Hoign6 (1985),
atrazine is degraded by the following reactions and
mechanism:
Direct reaction with ozone:

}'s I,, k ...

I o\

General mechanism o f the ozonation o f atrazine

kd

A -t- zO3-----*Interme&ates

12

16

20

24

28

(1)

where z is the stoichiometric ratio and kd the rate

constant of step (1), and by the action of hydroxyl
radicals:

time, rain

Fig. 2. Influence of hydroxyl radical scavengers on the

ozonation of atrazine. Variation of CA/CAo with time.
Po~= 1050Pa, CA0= 5 x 10-SM (average values).

A + OH kOH,A,Intermediates kOH,A
= l . 8 1 0 1 O M - J s I (2)
(Beltrfin et al., 1993a).

presence of t-butanol to check the importance of the

radical contribution to the elimination of atrazine.
The direct reaction of ozone and atrazine represented, as shown later, a 24 and 81% of the
elimination of atrazine in the absence and presence of
t-butanol (0.01 M in concentration and 20C), respectively. Now, it can be observed (see Fig. 3) that
an increase of temperature leads to an increase of the
degradation rate of atrazine.

At first sight, hydroxyl radicals come from the

decomposition of ozone through the following general mechanism (Staehelin and Hoignr, 1985) where
the rate constant units are in M -1 s ~ or s-l:
Initiation step:
03 + O H - k~~ 70, HOr + 02 .

(3)

Propagation steps:
pK = 4.8

1.0

,.,

He2.'

~'~

I-X *

....

o 20
m, 10
Q
3

;~'~'~

l '~
I- \ \

"

, O~. + H +

'~.~=.
" ~_~ff-,.~.

re,,_

1100
840
670

k I = 1.9 109

O~. + 03

, O;. + 02

*"..'-2"*'-

OO31' " 1100 Pae

T,*C

z~'~
~ ,,LU~,,~

2010

t II i

31

~..o

, HO3.

(6)

, OH. + 02

(7)

12

18 20
time, min

k 3 = 1.4 105

H e 3.

~ - - .

(5)

k 2 = 5 x 1010

O~. + H +

(4)

T *C PO31 Pa

I\~,-

2','~'8

Fig. 3. Influence of temperature on the ozonation of

atrazine. Variation of CA/CAo with time at pH 2,
CA0= 5 x 10-SM (in the presence of 0.01 M t-butanol at
different Po3i).

k 4 = 2 x 109

OH. + 03

, HOt + 02.

(8)

Termination steps [in addition to reaction (2)]:

ksi

OH. + Si

, final products?

(9)

Ozone oxidation of atrazine

15

being S~ a hydroxyl radical scavenger like t-butanol,

and
OH. + Intermediates kp, final
or more intermediate products?

C03 s - 1.1 x 10 - 4 M

~;

(10)

2157

**
~
~-~ ......

10

-!----~.--_

o
T*C

In the above mechanism some features have been

considered. First, ozone is a promotor of its own
decomposition through reactions (5) and (8). Second,
in the presence of scavengers of hydroxyl radicals,
S, the termination step could be the reactions of
hydroxyl radicals with atrazine and intermediates.
Third, intermediates or ozonation byproducts can
compete with atrazine for the ozone available
through their direct reactions (not considered). And
fourth, reactions between molecular compounds
(atrazine and intermediates) are considerred as termination steps of the main radical mechanism (Glaze
et al., 1992).
Determination o f the rate constant o f the direct reaction between atrazine and ozone, kd

7_-_ ~ .

Po3i,

Pa

:,

12

= 20

1100

* 10
o
3

840
695

16

20

24

28

t i m e , rain

Fig. 4. Changes of dissolved ozone concentration with time

during the ozonation of atrazine at pH 2 in the presence of
0.01 M t-butanol at different temperatures.

that necessary for ozone to reach its stationary

concentration, Co3s, then the oxidation of atrazine
follows a pseudo first order kinetics
For t t> ts

According to this mechanism the rate of atrazine

degradation has two contributions through reactions
(1) (direct way) and (2) (radical way)

dCa

dt = k'd CA

(13)

where
dCA
dt

kd
CA Co 3+ kon.ACA Coll.
z

(11)

k~ = k~ co.

(14)

where CA, Co3 and C o , represent the concentrations

of atrazine, dissolved ozone and hydroxyl radicals,
respectively. In equation (1 l) there is no volatilization
term since atrazine is a non-volatile compound, at
least for the short experimental reaction times of this
work.
In order to determine the direct rate constant, ko,
it is necessary to eliminate the contribution of
hydroxyl radicals. In so doing, a series of experiments
was performed at pH 2 in the presence of t-butanol
to decrease the action of radicals. This compound
reacts fast with hydroxyl radicals, the rate constant
of this reaction is 7.3 1 0 8 M - l s - I (Scholes and
Willson, 1967), and practically does not react
with ozone, the rate constant of its direct reaction
with ozone has been reported to be lower than
3 10-3M I s--I (Hoign6 and Bader, 1983a). A concentration of 0.05 M of t-butanol was applied to
ensure that all hydroxyl radicals formed are inhibited
by the scavenger, the initial atrazine concentration
being 4.8 x l0 -5 M. Under these conditions, the rate
of atrazine oxidation is

Equation (13) can be integrated under the following

boundary conditions

t=ts

CA=Cas

(15)

t=t

CA=CA

(16)

CAs being the concentration of atrazine when the

ozone concentration reaches its stationary value,
Co3s. After integration, the resulting equation is
In CA = -- k'd(t -- ts)

(17)

According to equation (17) a plot of ln(CA/CAs ) vs

( t - ts) should yield a straight line whose slope is

-0.1
~'~ -0.2

dCA = k d C A C o '
dt
z

(12)

Another particular feature of the ozonation of

atrazine, especially at pH 2, is that the dissolved
ozone concentration reaches its stationary and maximum value in hardly three minutes of reaction
(which is a strong indication of very slow gas-liquid
reaction) as shown in Fig. 4. If equation (12) is
applied to reaction times equal to or higher than

-0.3
i
0

3
10
20

"~

695
840
1100
i
8

-.,,,..
i

12

16

t - t s,

rain

=
20

,
24

,
28

Fig. 5. Verification of equation (17). Variation of

ln(CA/CAo ) with (t - t~) at different temperature, pH 2 and
in the presence of 0.05 M t-butanol. CA0= 4.8 x l0 -5 M.

2158

FERNANDOJ. BELTR~.Net al.

- k ~ . Figure 5 shows this plot corresponding to the

experiments carried out at different temperature (3,
10 and 20C), pH 2 and in the presence of 0.05 M of
t-butanol. It can be observed that points are situated
around straight lines whose slopes are negative and
increase (in absolute value) with the increasing temperature. By taking into account the values of Co3s
and z [the latter was found to be 1, calculated
following a procedure already published (Sotelo
et al., 1990)], the rate constant of the direct reaction
of atrazine and ozone was determined to be 4.5, 3.5
and 2.8 M -j s -~ at 20, 10 and 3C, respectively. From
these values the following Arrhenius function was
obtained
k d = l . 0 1 x 104exp(--18.8/RT), M - i s

i (18)

absence of scavengers are undoubtedly due to the

contributions of radical reactions which were not
inhibited during their experiments.
Modelling the ozonation o f atrazine in water
From the mechanism formed by reactions (1)-(10)
combined with mol balance equations of atrazine and
ozone (for the latter applied to the water and gas
phases) the concentration of these species can be
predicted for any set of experimental conditions.
Thus, the kinetic model equations are:
Mol balance of atrazine:
dCA =kdCACo3+koHACACoH.
dt

(23)

where the activation energy is in kJ.mol -~.

Since atrazine is a dissociating compound there are
in fact two direct reactions with ozone to consider;
those with its protonated and unprotonated forms
which are in equilibrium in water

Mol balance of ozone in water (assuming that gas

and liquid phases are well mixed in the reactor):

AH + ~ A + H +.

where KGa, Co3g, R, H and T are the overall gas

phase mass transfer coefficient, referred to the liquid
volume, the concentration of ozone in the gas leaving
the reactor, the gas and Henry law constants and
temperature, respectively, and/~ri the decomposition
term of ozone due to chemical reactions, defined,
neglecting the contribution of its direct reactions
with intermediates, as follows

(19)

Therefore, k d is expressed as a combination of the

rate constants of these reactions as follows
kd = kAH+Ct + kA(1 -- Ct)

(20)

where ct is the degree of protonation which is a

function of pH and pKa of equilibrium (19)
10-Prl
= 10_PH + 10_P~a.

dCo3
dt = KGa(Co3gRT - HCo3) - ,~ri

(24)

T,ri = (kdCA + ki 10(on - 14).~_kl Co2. + k4Cou. )Co3. (25)

(21)
Mol balance of ozone in the gas phase:

However, Hoign6 and Bader (1983b) have reported

that protonated amino compounds do not react
directly with ozone, so that equation (20) simplifies to

dC3~= Vvs \ R T

Co3g) - K G a ' ( C o , ~ R T - H C o 3 )

(22)

(26)

At pH 2 the degree of protonation of atrazine is

0.28, pKa = 1.6 as reported by Yao and Haag (1991),
and from equations (18) and (22), the actual rate
constant of the direct reaction between atrazine and
ozone at 20C is 6.3 M - i s ~. In fact, for pH >/4,
~ 0 and k d ~ kg, which is in accordance with the kd
value reported by Yao and Haag (1991) at pH 4.1 (see
Table 1). Comparing with other literature data, the
value of k d obtained in this work is something higher
than that reported by Xiong and Graham (1992)
which was obtained from competitive homogeneous
ozonation of atrazine and MCPA as reference compound. Deviations could probably be due to the fact
that the latter depends on the rate constant value of
the reaction between ozone and the reference compound. On the other hand, Xiong and Graham (1992)
also reports kd to be 12.2 M -~ s -~ at pH 7.5 obtained
in the presence of 10-4M of carbonate ion, a concentration which seems to be too low to inhibit all
hydroxyl radical formed at this pH. Finally, the
extremely high values reported by Adams et al. (1990)
and Adams and Randtke (1992) at any pH in the

where v0, Po3i and VG are the gas volumetric flow rate,
ozone partial pressure at the reactor inlet and the
accumulated volume of gas within the reactor
(50 cm3), respectively, and KGa' is the overall mass
transfer coefficient referred to the gas volume which
is related to KGa as follows

kd = ka(1 - ~).

vo

KGa = -~L K~a"

(27)

Ve being the liquid volume in reactor (800 cm3).

It has to be noticed that mol balance equations of
intermediates should be included in the kinetic model
since these compounds also consume hydroxyl radicals and ozone. However, as atrazine and intermediates have similar nature (Legube et al., 1987; Adams
and Randtke, 1992) their direct reactions will be
neglected because of their expected low contributions
to consume ozone. Consumption of hydroxyl radical
by intermediates, on the other hand, will be accounted for assuming a constant hydroxyl radical
scavenger contribution for atrazine and intermediates
during the reaction period as explained later. As

2159

Ozone oxidation of atrazine

a consequence, tool balance equations for intermediates were not considered.

Determination o f radical concentrations

Applying the hypothesis of the stationary state to
the net formation rates of radicals in the proposed
mechanism, the hydroxyl and superoxide ion radical
concentrations are finally expressed by the following
equation

COH'

2k i 10~PH- 14)Co3
kOH.ACA + ~kpi Cpi+ Zk~i C~i

(28)

Table 3. Hatta numbers of ozone decompositionreactions in the

ozonation of atrazinea
Reactionb
pH 2
pH 7
pH 12
Direct
5.410 -3
6.4x10 3
6.4xl0 3
Hydroxyl ion
initiation
5 x 10-6
1.6 x 10 3
5.2 x 10
Free radical
2.4 x 10 6 7.1 x 10 4
2.1 x 10
aHatta numbers calculated from equation (30). Conditions:
20C, CA0= 5 x 10 ~M; kL = 10 4ms- ~. bContribution of
terms of equation (31).
whose rate constants are, respectively, kd, 3k~ 10~pH- 14)
and
4k4k i 10(PH- 14)

and

koH. ACA + 2;kpi Cpi + Sksi Csi

2k i 10(PH- 141_[._k4 Con.

Co~. -

kl

Determination o f the kinetic regime o f absorption

It should be first noticed that the system formed
by equations (23)-(25) only holds if the reactions
through which ozone decomposes are slow relative to
the ozone mass transfer rate (Charpentier, 1981). This
fact can be checked by calculating the Hatta number
of these reactions, which relates the chemical reaction
and physical absorption rates within the diffusive film
in the proximity of the gas-water interface. For an
irreversible m,n order gas-liquid reaction, the Hatta
number is defined as follows

Ha =

= (klCo2. +k4Co,.)/Co~

(29)

(30)

kL

(32)

Applying equation (30) to these reactions their Hatta

numbers were calculated at different pH levels. First,
k L was taken to be 10 -4 ms -l, which is a typical value
for the type of contactor used in this work, and Do3
was obtained from bibliography (Matrozov et al.,
1976). Table 3 presents the results. It can be observed
that in all of the cases but one (at pH 12) Ha is well
below 0.3, condition for the reactions to be slow, and
hence the proposed mol equation system is applicable. At p H 12, however, the hydroxyl ion catalysed
decomposition reaction of ozone (initiation step in
the mechanism) is a moderate reaction, that is, part
of the dissolved ozone decomposes in the film layer.
As a consequence the kinetic model does not hold at
pH 12 and we have focused the attention on the
ozonation at p H 2 and 7.

Determination o f K6a
where m and n are the reaction orders with respect to
the gas being dissolved (ozone in our case) and a
compound or species B already present in the liquid
phase (atrazine, hydroxyl ion or a radical in our
case), k is the rate constant of the reaction considered,
Do3 the diffusivity of the dissolved gas in the liquid
and k L is the individual liquid phase mass transfer
coefficient.
The decomposition of ozone develops through four
different reactions [see equation (25)]. However, the
contributions of these reactions in equation (25), after
considering the stationary state hypothesis for hydroxyl and superoxide ion radicals [see equations (28)
and (29)], eventually become

In order to solve equations (23)-(26), it is necessary

to first calculate the overall mass transfer coefficient,
KGa, and express the concentration of hydroxyl and
superoxide ion radicals as a functions of the concentrations of stable species, such as atrazine, ozone and
scavengers. In an ozonation experiment when the
concentrations of ozone in the water and in the gas
leaving the reactor have reached their stationary
values, Co3s and Co3gs, respectively, K~a' can be
obtained from equation (26) where the ozone accumulation term is now zero due to the steady state
condition
t~ FPO3i
]
0 [_~-~ -- Co3~

KGa
'=

~ r i = [kdC A -4- 3k i 10(pH - 14)

VG ( Co, g~R T - H Co3s ) "

(33)

4k4ki 10ton -

14)C3

If

- - - - + ko..ACg + -ZkpiCoi
+ Sks, C~iJ

03

(31)

Table 4. Rate constants of reactions between the hydroxyl radical

and scavengers, k, used in this work
ksa

Equation (31) indicates that ozone decomposes

through three hypothetical reactions: an 1,1 order
direct reaction with atrazine (direct reactions between
ozone and intermediates have been neglected), a
pseudo first order hydroxyl ion catalysed reaction
and, finally, a pseudo second order radical reaction,

Species
(M - )s i)
t-Butanol
7.3 x l0s
Carbonate ion
4.2 x l0s
Bicarbonate ion
1.5 x l 0 T
Phosphoric acid
2 x 106
Diacid phosphate ion
2.2 x 106
Monoacid phosphate ion
8 105

Reference
Scholes and Willson (1967)
Weeksand Rabani (1966)
W e e k s and Rabani (1966)
Grabner et al. (1973)
Grabner et al. (1973)
Grabner et al. 0973)

FERNANDO J. BELTR./~N

2160

Table 5. Calculated ~ and experimental values o f COB and ?o~

CAo x 105
(M)
4.84
4.24
4.80
5.31
4.76
5.07f
4.98
5.34 g

C~

Experimental

pH

(M)

cOH b

~'O3

2
2
2
7
7
7
7
7

-0.01 d
0.05 d
-0.075 c
----

4.4 x 10-14
5.9 x 10 15
3.5 x l0 n
1.4 x 10-13
4.3x10-~4
4.6 x 10- ~4
1.2 x l0 -13
6.2 x 10 is

24
81
100
18
37
35
23
10

Calculated a

COB
1.6 x
1.9 x
4.1 x
1.3 x
5x
6.6 x
1.3 x
2.5 x

703

10-2 100
10 2t 100
l0 -22 100
10-15
96
10-16
98
10 - ~6 96
l0 -15
96
10 -15
96

~Obtained from the basic mechanism o f reactions (1)-(10); average

value of Po3~ is 1050 P a unless indicated, bFrom equation (41).
CFrom equation (39). at-Butanol concentration. ~rotal bicarbonate ion concentration, rPo3~ = 500 Pa. gPo3~= 2000 Pa.

The application of equation (33) to the ozonation

experiments yielded an average value for KGa' of
(4.7 _ 2.1) 10-3 mol - atm -~ (1 of gas) -I s -~. Now,
from equation (27) KGa was found to be
(2.9_+ 1.3) x 10 4 M - a t m - l s - l .
Prediction of concentrations of atrazine and ozone

At this stage, the first order differential equations

(23), (24) and (26) can be solved numerically to
obtain the concentration profiles of atrazine and
ozone. In this work, the fourth order Runge-Kutta
method was applied, solving the system with the
initial conditions
t=0

CA=C ~

Co~=0

and

Co3g=0.

(34)

Due to the unknown composition of the ozonated

atrazine solution at any time, in the denominator of
equation (28) the scavenger term of atrazine and
intermediates [reactions (2) and (10)] was assumed to
be constant and expressed as
kOH, A C A q-

,~kpiCpi

= kOH, A CA0.

(35)

This is a reasonable hypothesis if the following

circumstances are considered or assumed:
1. The rate constants, kOH,A and kpi, of hydroxyl
radical reactions can be approximately equal because
the unselective character of hydroxyl radicals [the
rate constants of these reactions are of similar magnitude, Farhataziz and Ross (1977)] and the intermediates formed during the ozonation of atrazine, as
reported by Legube et aL (1987) and Adams and
Randtke (1992), are also similar in nature to their
parent compound, atrazine.
2. Total mol balance of atrazine and intermediates
holds at any time during the reaction period considered in these experiments. It has to be noticed
that Adams and Randtke (1992) reports that
mineralization is negligible which supports the above
comment.
For solving the system, the values of ksi applied are
given in Table 5 and the Henry constant was obtained
from a previous work (Sotelo et al., 1989). Under
these conditions and hypothesis, however, the model
overestimated the experimental concentrations except
when a high concentration of scavenger was present.

et al.

For this case, Fig. 6 presents the variation of calculated and experimental concentrations of atrazine
and ozone in water and in the exiting gas for the latter
versus reaction time. This suggests that the model
works well when hydroxyl radical reactions are suppressed. The results obtained at other conditions,
however, can be surprising at first sight, since mol
balances of intermediates were not included. Under
these circumstances, it should be expected the calculated concentrations of atrazine to be lower than the
actual values because intermediates also consume
ozone and hydroxyl radicals and their contribution
would tend to stabilize the concentration of atrazine.
It could seem that the hypothesis given by equation
(35) is the reason of the high values calculated for the
concentrations of atrazine. However, solution of
differential equations (23), (24) and (26), considering
only the role of atrazine as hydroxyl radical scavenger, that is, kOH, A C A instead of kOH,ACAo in
equation (35), leads to high calculated concentrations
as well. There can be different explanations to this
behaviour. Thus, atrazine and some ozonated byproducts could be promoters of hydroxyl radicals
if their reaction with these radicals eventually release
the superoxide ion radical, as reported by Staehelin
and Hoign6 (1985) for some compounds. However,
the promoting character of intermediates have
also been considered when equation (35) was not
applied. Furthermore, if atrazine is also a promotor
of hydroxyl radicals, in the absence of scavengers,
the only possible termination step would be the
reaction between hydroxyl radicals (Staehelin et al.,
1984)
kt=Sxl09 M I s I

OH" + OH"

, H,O2

(36)

Note that reaction between ozone and hydroxyl

radical is not a termination step but a propagation
reaction. According to all this, the concentration
of hydroxyl radicals could be given by equation
(37)

[2k~lO C~"- ~4~C 705

Co. = L

kt

3/

(37)

However, for an average concentration of ozone of

10-SM and pH 7 equation (37) leads to a concentration of hydroxyl radicals of 1.7 x 10 -j M which is
too high compared to the experimental values obtained as shown later.
Another possible explanation to the differences
between predicted and experimental concentrations
of atrazine can be due to the presence of traces of
impurities in the starting material that, acting as
initiators, could have promoted the decomposition of
ozone into radicals, a role that has also been attributed to some substances (Staehelin and Hoign6,
1985). In this case, the following reaction should be
considered
hi

I + O3---+O3. -+ OH"

Ozone oxidation of atrazine

While solving the simultaneous differential

equations of the kinetic model )'o3 was obtained to be
100% at pH 2 and 96% at pH 7. These results
together with the predicted concentration of hydroxyl
radicals obtained from equation (28) are given in
Table 5.
On the other hand, the experimental values of
Vo3and Con. were obtained as follows. If it is assumed
a constant concentration of dissolved ozone, Co3m,
for the whole reaction period (which is true after a
few minutes of the start of ozonation) and the
stationary hypothesis for the hydroxyl radical holds
(thus, Con. is constant), the rate of disappearance of
atrazine is

so that the concentration of hydroxyl radicals becomes

(2ki 10(PH- 14)+ kl Cl)Co3
COH" ~---

koH, A CA, + ~kp~Cpi + Y,k~C~i

(2k~ 10CpH- 14)C03+ #

(38)

koH, ACAo + Z'ksiCsi

where the term fl is a hydroxyl radical initiating rate

factor that would involve other contributions to the
formation of hydroxyl radicals apart from the initiation step [reaction (3)]. This term would depend
on the experimental conditions and composition of
the starting aqueous solution.

Direct and radical contributions to the oxidation of

atrazine

dCA

dt - (kdC3m + kOH'ACoH')CA = kTCA (40)

An important feature of this process is to know the

contribution of the direct and radical ways to the
elimination of atrazine that, on the other hand, is
related to the initiating rate factor, ft. Thus, the
percentage elimination of atrazine through its direct
reaction with ozone is

kdC3

x 100.

2161

Integration of equation (40) leads to the determination of k v and hence to the experimental
hydroxyl radical concentration

(39)

CoHexp=

~o3 = kd Co 3+ kor~,ACon.

kT -- kd Co3m
koH,A

(41)

1.0~
B

I:

b
1(~

:f

0.5

'

'

' t~

' lh

' ~o'

~4'

18

'

,2

time, rain

(a)

2o

24

28

(b)

o
o

Calculated

16
tlrr~, m~

data

O~

i
4

i
8

,
12

16

,
20

i
24

28

time, rain

(c)

Fig. 6. Checking of the ozonation kinetic model. Variation of experimental and calculated concentrations
with time: (a) atrazine as CA/CAo; (b) dissolved ozone; (c) ozone in the gas. Conditions: pH 2,
CA0= 5 X 10-5 M, 0.05 M t-butanol, Po~ = 1100 Pa.

2162

FERNANDOJ. BELTRANet

Table 6. Values of the hydroxyl radical initiating rate factor, #, at

different experimental conditions

CA0 10s

C,

#~

(Pa)

Po~,
pH

(M)

(M)

(M s - i )

1020
1100
I100
1020
1020
500
1000
2000

2
2
2
7
7
7
7
7

4.8
4.2
4.8
5.3
4.8
5.1
5.0
5.3

-0.01 b
0.05 b

4.05
4.8
1.3
1.32
7.75
4.00
1.06
5.50

--

0.075
----

x
x
x

x
x
x

of some impurities at trace concentration. In fact,

both factors are accounted for in the term fl that can
be calculated once Co.. is known, by the following
equation

10 - s
10 - I
10 -
10 _7
10 - ~
10 - s
10 - 7
10 - 7

fl = (koH,ACA0+

Table 5 also shows the experimental values of Coll.

calculated from equation (41). Comparing with the
predicted values one can observe important differences. Also, shown in Table 5 are the experimental
values of Yo3 obtained from equations (41) and (39).
These results show the importance of radical reactions even at pH 2 in the absence of scavengers.
According to them, in addition to reaction (3),
there have to be other routes to form hydroxyl
radicals. These can be due to the promoting character
of some intermediates and/or to the initiating effect

SksiCsi)Cou.

2ki 10<pH-14)Co3 (42)

Table 6 presents the values of # obtained at

different conditions; they are practically constant
with time but vary with pH and concentration and
nature of hydroxyl radical scavengers. Since intermediates are different depending on the presence or
absence of scavengers as can be deduced from the
work of Adams and Randtke (1992) fl can involve the
hydroxyl radical promoting character of some intermediate compounds.
Values of fl were included in the kinetic model to
compensate the formation of hydroxyl radicals
through routes different to reaction (3). The differential equations (23), (24) and (26) were again solved
numerically to calculate the new predicted concentrations of atrazine and ozone. Figures 7 and 8
show some of the results obtained together with the
experimental ones. It can be observed that the
model predicts the experimental concentrations with

~Calculated from equation (42). bt-Butanol concentration. ~l'otal

bicarbonate ion concentration.

1.0

al.

Wlth s c a v e n g e r

l
C,, M

II

10
pH 2

B---'-~
o

Calculated

0.01

data

4
5
O

Calculated d a t a
t-butano~
C,, M
pH 2

i16

12

20

24

28

12

16
20
time, rain

time, mln

(a)

Io

Wlth s c a v e n g e r
'

,/
n

"1

0.01

28

(b)
n

Calculated

(-> 2

24

data

t-bulanol
C,, M
pH 2
0e

112

16
tlme, mTn

24

0.01

28

(c)
Fig. 7. Checking of the ozonation kinetic model with the inclusion of ft. Variation of experimental and
calculated concentrations with time at pH 2: (a) atrazine as CA/CAo;(b) dissolved ozone; (c) ozone in the
gas. Po~i = 1060 Pa, CA0 = 4.8 x 10 -5 M.

Ozone oxidation of atrazine

2163

1.0

IO
~

pH 7

0.075

w,,.T_
u

u'

3"
Bf~rbonotoion
F7
I

C~.M
mm

pH 7

12

16

20

24

28

12

time, rain

(a)

24

28

(b)

with sottvenger

20

time. rain

Calculeteddata
o

16

0.07S

t'

Bicarbonate Ion

C=,M
pH 7

12

16

0.075

24

28

time. rain

(e)
Fig. 8. Checking of the ozonation kinetic model with the inclusion of ft. Variation of experimental and
calculated concentrations with time at pH 7: (a) atrazine as CA/CAo; (b) dissolved ozone; (c) ozone in the
gas. Po3i= 1020Pa, CA0= 5.3 x l0 -5 M.

deviations lower than 15% except those of dissolved

ozone in the absence of scavengers. Deviations between experimental and calculated values of dissolved
ozone concentration could be due to the consumption
of ozone in direct reactions with some intermediates
that were not accounted for. These reactions do not
likely develop in the presence of scavengers since the
nature of intermediates can be different (Legube
et al., 1987; Adams and Randtke, 1992).
CONCLUSIONS

The ozonation of atrazine is a process that at

neutral pH develops mainly through radical reactions. The total rate constant of the direct reaction
with ozone is very low (6.3 M -l s -I at 20C) so that
even at pH 2 the contribution of the radical way can
be important. In addition, the process is highly
dependent on the presence of impurities that promotes the decomposition of ozone and/or the promoting character of some intermediates able to
release superoxide ion radicals and hence hydroxyl
radicals. The lack of knowledge of these contributions can be grouped in a term called the hydroxyl
radical initiating rate factor. Inclusion of this factor
in a kinetic model formed by mol balance equations
WR 28/1(~-I

of atrazine and ozone, once the decomposition of the

latter due to chemical reactions is obtained from
applying the mechanism of Staehelin and Hoign6
(1985), considerably improves the concordance between predicted and experimental concentrations
especially when the presence of a strong hydroxyl
radical scavenger is considered in the model. The
more important discrepancies are observed when
comparing the experimental and calculated concentrations of dissolved ozone in the absence of scavengers. This could be attributed to the appearance of
some reactive intermediates towards ozone. As a
consequence further studies to elucidate these reactions and competitivity of intermediates especially for
the ozone available are needed to complete the full
mechanism of the ozonation of atrazine.
It should be noticed that in a real situation with
a surface water, contaminated by atrazine or a
given pollutant, carbonate/bicarbonate ions would be
likely present, possibly at appreciable concentration
( > 10-4 M). Since the full composition of the aqueous
ozonated solution is not possible to know and ozonation is going to be applied, the model used in this
work could be adopted. Thus, once the initiating rate
factor is calculated as shown in this work and introduced in the kinetic model, the concentration of the

FERNANDO J. BELTK.AN et al.

2164

remaining atrazine or a given pollutant, for a n ozone

dose applied, can be predicted.
Acknowledgement--Authors thank the CICYT of Spain for
its support through grant AMB93/654.

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