The influence of water quality parameters (dissolved organic matter and alkalinity) on the

efficiency of the ozone/hydrogen peroxide (O3/H2O2) advanced oxidation process (AOP)

relative to the corresponding conventional ozonation process was investigated. In natural
waters with a high natural organic matter content (ⱖ3 mg/L), O3 decomposition is controlled
BY JUAN L. ACERO by radical-type chain reactions. Thus, the overall OH radical oxidation capacity is nearly
AND URS VON GUNTEN independent if conventional ozonation is replaced by O3/H2O2 AOP. In contrast, when the

organic matter content in the natural water is low (ⱕ1 mg/L), the addition of H2O2 considerably

enhances the oxidation capacity by OH radicals. A constant ratio between the OH radical
and O3 concentration (Rct) was found during both treatments, making it possible to predict
the oxidation of micropollutants with O3 and OH radicals if the rate constants of both oxidants
are known. The oxidation of atrazine during ozonation and the combined process O3/H2O2
could be accurately predicted in natural waters.

CHARACTERIZATION OF

OXIDATION
processes:
ozonation and the AOP O3/H2O2
hen drinking water is ozonated, it is often difficult to maintain a suf-

W
ficient level of disinfection and pollutant removal while limiting the
formation of disinfection by-products (DBPs), in particular bromate.
Ozone (O3) is an efficient disinfectant (J.M. Montgomery Engi-
neers, 1985) and a very selective oxidant (Hoigné & Bader, 1983a;
Hoigné & Bader, 1983b; Hoigné et al, 1985), being relatively unreactive toward
many inorganic and organic compounds. When O3 decomposes in aqueous
solution, it forms, among other secondary oxidants, hydroxyl radicals (·OH). ·OH
is an extremely powerful and nonspecific oxidant that reacts with both organic
and inorganic species, with rate constants ranging from 108 to 1010 M–1 s–1
(Haag & Yao, 1992). With respect to disinfection, ·OH plays a minor role rel-
ative to O3 because of its low, transient, steady-state concentration, which
results from high reactivity with water matrix components. To reinforce oxidation
by ·OH with the purpose of micropollutant control, advanced oxidation processes
(AOPs) are applied. The ozone/hydrogen peroxide (O3/H2O2) combination is the

©2001 American Water Works Association

90 OCTOBER 2001 | JOURNAL AWWA | PEER-REVIEWED | ACERO ET AL
FIGURE 1 Depletion of O3 for conventional ozonation (O3) FIGURE 2 O3 exposure for conventional ozonation (O3)
and the O3/H2O2 process in a groundwater and the O3/H2O2 process in a groundwater
and a surface water and a surface water

20

100

O3, GW
15 80

O3, GW

O3 Exposure—(mg/L) .min
60
O3—µM

AOP, GW 10
10

O3 Exposure—(mg/L) .min
8 AOP, GW

40 6
O3, SW
O3, SW
4
5 AOP, SW
20 2
AOP, SW

0
0 20 40
Reaction Time—min
0 0
0 20 40 60 80 100 120 0 50 100 150 200 250 300

Reaction Time—min Reaction Time—min

o
Experimental conditions—pH = 7, temperature = 11 C, [O3 ]0 = The inset is a magnification of the initial phase. Experimental
–5 –5 o
2.1 ✕ 10 M, [H2O2 ]0 = 1.0 ✕ 10 M, [pCBA]0 = 0.25 µM conditions—pH = 7, temperature = 11 C, [O3 ]0 =
–5 –5
AOP—advanced oxidation process, GW—groundwater, 2.1 ✕ 10 M, [H2O2 ]0 = 1.0 ✕ 10 M, [pCBA]0 = 0.25 µM
H2O2—hydrogen peroxide, O3—ozone, pCBA—p-chlorobenzoic AOP—advanced oxidation process, GW—groundwater,
acid, SW—surface water H2O2—hydrogen peroxide, O3—ozone, pCBA—p-chlorobenzoic
acid, SW—surface water

most widely applied AOP in drinking water treatment
(Duguet et al, 1985) because conventional ozonation
processes adapt relatively easily to an AOP by addition
of H2O2.
The addition of H2O2 to accelerate the decomposi-
tion of O3 into ·OH is recommended for waters in which
O3 is relatively stable (i.e., low organic matter content
and high alkalinity) (Griffini & Iozzelli, 1996). There-
fore, the application of O3/H2O2 leads to an increased
transformation of O3 into ·OH for a given hydraulic res-
idence time (HRT), even if high O3 dosages are applied.
Any excess H2O2 is eliminated by biological processes
during postfiltration using anthracite or granular acti-
vated carbon (Urfer & Huck, 1997).
An undesirable consequence of increasing O3 dosages
to optimize an AOP with respect to micropollutant oxi-
dation is increased DBP formation from the natural
organic matter (NOM) present in the water (Glaze &
Weinberg, 1993) and the formation of bromate and
brominated organic compounds if bromide-containing
waters are being treated (von Gunten & Hoigné, 1994).
The difficulty of minimizing bromate formation (O3
and ·OH) while removing O3-resistant micropollutants
(oxidation by ·OH) has been shown (von Gunten &
Hoigné, 1994; von Gunten et al, 1996; von Gunten &
Oliveras, 1998; Lefevre & Deguin, 1997). Consequently,
application of the O3/H2O2 process must be carefully
optimized with respect to oxidation capacity (high oxi-
dant exposure) and DBP formation (low oxidant expo-
sure) in order to fulfill all water quality requirements
(WHO, 1993). In addition, if disinfection is an issue, a
high O3 exposure is required. To optimize these treat-
ment goals, knowledge of the oxidant concentrations
throughout the process is required.
MEASURING ·OH CONCENTRATION
O3 concentration can be measured directly by elec-
trochemical or colorimetric methods (Langlais et al,
1991). However, there is no fast and easy method for
directly measuring ·OH concentration in situ. Attempts
at predicting ·OH concentrations from O3 decomposition
have been made using computer models (Tomiyasu et
al, 1985; Westerhoff et al, 1997). A kinetic model for
the O3/H2O2 process has been applied in a defined lab-
oratory system using distilled water (Acero & von Gun-
ten, 2000). The influence of carbonate, promoters and
inhibitors, in simulating the natural matrix of drinking
water on O3 decomposition, ·OH oxidation capacity,

©2001 American Water Works Association

ACERO ET AL | PEER-REVIEWED | JOURNAL AWWA | OCTOBER 2001 91
FIGURE 3 First-order kinetic representation for O3 depletion FIGURE 4 Relative decrease in pCBA as a function
in a groundwater and a surface water for conventional of the reaction time during conventional
ozonation (O3) and the O3/H2O2 process ozonation (O3) and the O3/H2O2 process

0 1.0

–0.5
O3, GW
0.9 HRT in ozonation
–4 –1
k = 1.5 ✕ 10 s reactor = 15 min
–1.0

0.8

Relative Decrease of pCBA

–1.5
O3, GW
In([O3]/[O3]0)

–2.0 AOP, GW 0.7 O3, SW

AOP, SW
–3 –1
k = 1.4 ✕ 10 s

–2.5
0.6
5h
–3.0
0.5

–3.5
O3, SW
–3 –1
k = 2.5 ✕ 10 s 0.4
–4.0 AOP, SW AOP, GW
–3 –1
k = 5.8 ✕ 10 s

–4.5 0.3
0 20 40 60 0 20 40 60

Reaction Time—min Reaction Time—min

o
Experimental conditions—pH = 7, temperature = 11 C, [O3 ]0 = Data for a groundwater and a surface water are shown.
–5 –5 o
2.1 ✕ 10 M, [H2O2 ]0 = 1.0 ✕ 10 M, [pCBA]0 = 0.25 µM. Experimental conditions—pH = 7, temperature = 11 C, [O3]0 =
–5 –5
AOP—advanced oxidation process, GW—groundwater, 2.1 ✕ 10 M, [H2O2]0 = 1.0 ✕ 10 M, [pCBA]0 = 0.25 µM.
H2O2—hydrogen peroxide, O3—ozone, pCBA—p-chlorobenzoic AOP—advanced oxidation process, GW—groundwater,
acid, SW—surface water HRT—hydraulic residence time, H2O2—hydrogen peroxide,
O3—ozone, pCBA—p-chlorobenzoic acid, SW—surface water

and H2O2 consumption has been successfully modeled.
However, because of the complexity of the inorganic and
organic matrixes of natural waters, even well-established
models fail to adequately predict O3 decomposition with-
out fitting parameters into these systems. Even more dif-
ficult is the prediction of ·OH concentration. In the lit-
erature, no attempts have been made to experimentally
calibrate the model calculations (Tomiyasu et al, 1985;
Westerhoff et al, 1997).
An experimental approach to measuring the transient
concentrations of both ·OH and O3 during an ozonation
process has been developed by Elovitz and von Gunten
(1999). A new parameter, Rct, has been defined as the
ratio between the ·OH exposure and O3 exposure (i.e., the
concentration of oxidant integrated over the reaction
time). The method is based on measurement of the
decrease of an O3-resistant probe compound, which pro-
vides a measurement of the ·OH exposure. The Rct makes
it possible to determine the ratio of ·OH and O3 concen-
trations for the entire ozonation process. As a result, the
oxidation of micropollutants can be completely described
in bench-scale experiments if the corresponding rate con-
stants for oxidation with O3 and ·OH are known. The
authors’ main objective was to describe the O3/H2O2
process with respect to the oxidation by O3 and ·OH by
applying the Rct concept.
The transformation of O3 into ·OH is a complicated
reaction sequence, which can be roughly divided into ini-
tiation, promotion, and inhibition reactions. O3 decom-
position is initiated by hydroxide (OH–), the deproto-
nated form of hydrogen peroxide (HO2–), and some
organic compounds of the NOM water matrix (initia-
tion reactions) (Staehelin & Hoigné, 1982). The initiation
leads to the formation of ·OH, which then undergoes fur-
ther reactions (promotion and inhibition). Promotion of
O3 decomposition can be observed if ·OH is scavenged by
the NOM and thereby produces superoxide radicals
(HO2·/O2·–). These superoxide radicals react quickly with
O3 to ·OH. This chain reaction continues until ·OH scav-
enging by an inhibitor, which is a compound that does not
release superoxide and therefore does not lead to further
acceleration of O3 decomposition.

©2001 American Water Works Association

92 OCTOBER 2001 | JOURNAL AWWA | PEER-REVIEWED | ACERO ET AL
FIGURE 5 Rct-value calculations for conventional FIGURE 6 First-order kinetic representation for O3 depletion
ozonation (O3) and the O3/H2O2 process for two waters in a groundwater with varying concentrations
of DOC (1 and 2.2 mg/L)

0
0

–0.5
O3, GW
–0.2 –10
Rct = 7.9 ✕ 10 –1.0 O3, DOC 1 mg/L
–4 –1
k = 1.7 ✕ 10 s
–1.5
–0.4 O3, SW
–9
Rct = 8.1 ✕ 10

In([O3]/[O3] 0)
In([pCBA]/[pCBA] 0)

–2.0 O3, DOC 2.2 mg/L

–3 –1
k = 1.0 ✕ 10 s

–0.6 –2.5
AOP, GW
–8 –3.0
Rct = 1.4 ✕ 10
AOP, DOC 2.2 mg/L
–0.8 –3 –1
k = 4.4 ✕ 10 s
–3.5

AOP, SW
–4.0
–1.0 AOP, DOC 1 mg/L
–3 –1
k = 2.2 ✕ 10 s
–8
Rct = 2.2 ✕ 10 –4.5
0 20 40 60
–1.2 Reaction Time—min
0 0.01 0.02 0.03 0.04 0.05
Data for conventional ozonation (O3) and the O3/H2O2 process are
O3 Exposure—M.s o
shown. Experimental conditions—pH = 7.2, temperature = 11 C,
–5 –6
o [O3 ]0 = 1.5 ✕ 10 M, [H2O2]0 = 7.0 ✕ 10 M, [pCBA]0 = 0.25 µM.
Experimental conditions—pH = 7, temperature = 11 C, [O3 ]0 =
–5 –5 AOP—advanced oxidation process, DOC—dissolved organic
2.1 ✕ 10 M, [H2O2]0 = 1.0 ✕ 10 M, [pCBA]0 = 0.25 µM.
carbon, H2O2—hydrogen peroxide, O3—ozone, pCBA—
AOP—advanced oxidation process, GW—groundwater,
p-chlorobenzoic acid
H2O2—hydrogen peroxide, O3—ozone, pCBA—p-chlorobenzoic
acid, SW—surface water

In natural water, the primary inhibitors are NOM KINETIC FORMULATION

and carbonate/bicarbonate. In the O3/H2O2 process, To calibrate AOPs with respect to O3 and ·OH con-
the O3 chain decomposition cycle is initiated predom- centrations, an indirect method, based on measure-
inantly by HO2–. This is in contrast to the conventional ment of a decrease of an O3-resistant probe compound
ozonation process in which OH – and organic com- that reacts quickly with ·OH, was applied (Elovitz &
pounds of the natural water matrix initiate O3 decom- von Gunten, 1999; Haag & Yao, 1993). This mea-
position. The change in the initiating reaction for O3 surement allows transient, steady-state ·OH concen-
decomposition (from OH– to HO2–) may lead to dif- trations in aqueous solutions to be calculated. The
ferences in the yield of ·OH from O3. However, if rad- probe compound selected was p-chlorobenzoic acid
ical-type chain reactions that promote O3 decomposi- (pCBA), with a rate constant of kOH,pCBA = 5.2 3 109
tion are the major pathway for the decomposition of O3 M–1 s–1 for its reaction with ·OH and a rate constant
to ·OH, the addition of H2O2 may lead to an accelera- of kO 3,pCBA = 0.15 M–1 s–1 for its reaction with O3
tion of the O3-to-·OH process but only a small change (Yao & Haag, 1991). pCBA has a pKa of 4 (Yao &
in the overall ·OH yield. Haag, 1991); therefore, the rate constants are given
In order to calibrate different natural waters with for the deprotonated form. pCBA is used in very low
respect to their transient steady-state ·OH and O3 con- concentrations to prevent a significant contribution to
centrations and respective oxidation capacities, the influ- the overall scavenging of ·OH. The term “·OH oxida-
ence of carbonate content and NOM source on the ·OH tion capacity” is defined by the relative elimination of
and O3 concentrations was tested. The effects of the ratio the ·OH probe compound.
[H2O2]/[O3] on ozone decomposition and micropollu- The rate of pCBA oxidation, which reacts only with
tant elimination are also discussed. ·OH, is given by:

©2001 American Water Works Association

ACERO ET AL | PEER-REVIEWED | JOURNAL AWWA | OCTOBER 2001 93
 water. Concentrated O3 stock solu-
TABLE 1 Water quality parameters and their influence on O3 decomposition kinetics,
relative elimination of pCBA, and Rct*† tions were produced by continuously
bubbling O 3 -containing oxygen
[H2O2]0 ⌬H2O2‡ k(k sec)§ % Elimination
through double-distilled water that
M µM s –1 pCBA Rct (Rct sec)** was cooled in an ice bath (Hoigné &
Groundwater (DOC = 1.0 mg/L, alkalinity = 5.2 mM)
Bader, 1979). The concentration of
the resulting stock solution was
0 3.9 X 10–4 (1.5 X 10–4) 44 4.1 X 10–9 (7.9 X 10–10)
approximately 1.2 mM (60 mg/L).
1.0 X 10 –5 6.5 1.4 X 10 –3 66 1.4 X 10–8
Experimental methods. Samples of
Surface Water (DOC = 3.2 mg/L, alkalinity = 3.8 mM) natural water (groundwater and sur-
0 2.5 X 10 –3 28 8.1 X 10 –9 face water) were collected from two
1.0 X 10 –5 1.2 5.8 X 10 –3 29 2.2 X 10 –8 locations, filtered through a 0.45-µm
filter made of cellulose nitrate,* and
*O3—ozone, pCBA—p-chlorobenzoic acid, DOC—dissolved organic carbon, H2O2—hydrogen peroxide
†Experimental conditions were as follows: pH = 7, temperature = 11oC, [O3]0 = 2.1 X 10–5 M, [pCBA]0 = stored at 4oC until use. The ground-
0.25 µM.
‡⌬H2O2—consumed H2O2
water (from Porrentruy, Switzerland)
§k sec—first-order rate constant for O3 decay during the secondary phase of the reaction was characterized by low dissolved
**Rct sec—Rct-value during the secondary phase of the reaction
organic carbon (DOC) (1 mg/L) and
high alkalinity (5.2 mM HCO3–).
–d[pCBA] The surface water (from River Seine,
ᎏᎏ = k·OH,pCBA [pCBA] [·OH] (1) Paris, France) had high DOC (3.2 mg/L) and low alka-
dt linity (3.8 mM HCO3–). Reaction solutions were pre-
Rearranging and integrating Eq 1 results in: pared by adding H2O2 and buffer (10 mM borate) to the
filtered natural water and adjusting to the desired pH
with sodium hydroxide or hydrochloric acid. pCBA was
冢 冣 冕
[pCBA]t t
ln ᎏ ᎏ = –k·OH,pCBA [·OH]dt (2) added to the solution (0.25 µM) as the probe compound.
[pCBA]0 0
In addition, atrazine was added (0.25 µM) in some exper-
iments to represent a typical micropollutant. After adding
There is a correlation between the exposure of OH and · a concentrated O3 solution to achieve the desired O3
O3 (i.e., the concentration of oxidant integrated over the dose, samples were withdrawn using a dispenser system
reaction time), which is defined as Rct (ratio of C 3 T val- (Hoigné & Bader, 1994), quenched with indigo (Bader &
ues) (Elovitz & von Gunten, 1999): Hoigné, 1981), and analyzed as described later. The tem-
perature was kept constant at 11 ± 0.2oC to simulate
·OH – exposure 冕 [·OH]dt drinking water treatment conditions.
Rct = ᎏᎏ = ᎏᎏ (3) Analytical methods. Dissolved O3 was analyzed using
O3 – exposure
冕 [O3]dt the indigo method (Bader & Hoigné, 1981). H2O2 was
determined using the peroxidase-DPD method (Bader et
·
Substituting OH exposure from Eq 3 in Eq 2 gives: al, 1988). Solution pH was measured using a combination
pH electrode,† which was calibrated with standard
buffers.‡ pCBA was determined using reverse-phase high-
冢 冣 冕 t
[pCBA]t
ln ᎏᎏ = –k·OH,pCBA Rct [O3]dt (4) pressure liquid chromatography (HPLC)§ with an elu-
[pCBA]0 0
ent containing 45% 10-mM H3PO4 and 55% methanol
at 1 mL/min and detected at 234 nm. Atrazine was mea-
This allows the calculation of the Rct from the exper- sured using HPLC** with a mixture of 50% methanol
imentally measured decrease in concentration of pCBA and 50% 5-mM tetrabutyl ammonium hydrogen sulfate
and O3 (by plotting the ln([pCBA] t /[pCBA] 0 ) versus O 3 (TBAHS) in 10-mM phosphate buffer as eluent and
exposure). detected by its ultraviolet absorbance at 221 nm. The
If Rct remains constant during ozonation, it represents quantification limit was 0.025 µM for both compounds
the ratio between the concentrations of ·OH and O3 dur- with a 250-µL injection loop.
ing the ozonation process. Therefore, the concentration
of ·OH can be easily calculated from the measured O3
concentration.
*Sartorius AG, Goettingen, Germany
†Metrohm LTD, Herisau, Switzerland
EXPERIMENTAL METHOD ‡Titrisol, Merck KGaA, Darmstadt, Germany
Materials. All chemicals were reagent grade or analytical §Column: Merck Lichrospher 100, RP 18-5 µm, Merck KGaA, Darm-
stadt, Germany
grade, when available, and were used without further purifi- **Hypersil octadecylsylane (ODS), 5-µm column, Florio AG, Therwil,
cation. Stock solutions were prepared in double-distilled Switzerland

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94 OCTOBER 2001 | JOURNAL AWWA | PEER-REVIEWED | ACERO ET AL
 TABLE 2 Effect of [H2O2]0 and the ratio [H2O2]/[O3] on O3 decomposition kinetics, O3 exposure, relative elimination of pCBA, and Rct*†

[H2O2]/[O3] [H2O2]0 [H2O2]F k (k sec)‡ 冕 [O3]dt % Elimination

w/w (mol/mol) M M s–1 M·s pCBA Rct (Rct sec)§

0 (0) 0 0 1.7 X 10–4 0.31 49 3.3 X 10–9

(8.0 X 10–5) (4.2 X 10–10)
0.19 (0.27) 6.1 X 10–6 0.2 X 10–6 6.7 X 10–4 4.6 X 10–2 72 1.3 X 10–8
(3.0 X 10–4) (5.0 X 10–9)
0.34 (0.48) 1.1 X 10–5 3.7 X 10–6 1.2 X 10–3 1.7 X 10–2 76 1.5 X 10–8
0.7 (0.99) 2.2 X 10–5 1.4 X 10–5 2.8 X 10–3 8.2 X 10–3 78 3.5 X 10–8

*H2O2—hydrogen peroxide, O3—ozone, pCBA—p-chlorobenzoic acid

†Experimental conditions were as follows: groundwater (dissolved organic carbon 0.9 mg/L, alkalinity 5.2 mM), pH = 7.2, temperature =
11oC, [O3]0 = 2.3 X 10–5M, [pCBA]0 = 0.25 µM.
‡k sec—first-order rate constant for O3 decay during the secondary phase of the reaction
§ Rct sec—Rct-value during the secondary phase of the reaction

RESULTS AND DISCUSSION For disinfection as well as for many oxidation

Water quality parameters. The AOP O3/H2O2 was com-
pared with the corresponding conventional ozonation
process to assess its efficiency. To characterize both oxida-
tive systems, two water types that represent the range of
O 3 stability (groundwater and surface water) were
selected. This allowed the authors to assess the role of
NOM and alkalinity with regard to O3 stability, ·OH
oxidation capacity, and Rct.
Ozone stability. Figure 1 shows the evolution of the
O 3 concentration in experiments carried out in the
absence of H2O2 and in the presence of H2O2 with both
waters (1 mg/L O3, pH 7, 11oC). In the groundwater,
which had low DOC and high alkalinity, O3 was very sta-
ble during the conventional ozonation process. Bicar-
bonate/carbonate is known to inhibit O3 decomposition
(Staehelin & Hoigné, 1985), which leads to consider-
able stabilization of O3 in combination with the low
DOC concentration. The addition of H 2 O 2 (0.34 g
H2O2/g O3) accelerates O3 decomposition significantly.
The deprotonated form of H2O2 (HO–2) initiates the
degradation of O3, leading to the formation of ·OH (Stae-
helin & Hoigné, 1982). In this water, the initiation
became the dominant mechanism for O3 decomposition
(Staehelin & Hoigné, 1985).
Different behavior was observed in the surface water.
During conventional ozonation, O3 was much less stable
in this water, primarily because of promotion by NOM,
which results in an acceleration of the chain cycle for O3
decomposition. Therefore, the addition of H2O2 only
leads to a small difference if conventional ozonation and
AOP are compared. The effect of H2O2 addition on O3
stability was much less pronounced in the surface water
than in the groundwater. Even though H2O2 increased
the rate of O3 transformation during the initiation step,
the promotion by NOM was still the primary process for
O3 decomposition. Therefore, it can be qualitatively con-
processes, molecular O3 is the primary reactant. Figure 2
shows the O3 exposure in the experiments that used both
waters. The addition of H2O2 led to significantly lower
O3 exposures, especially in the groundwater (O3 exposure
was tenfold lower during the AOP). The O3 exposure
for the surface water varied only by a factor of about 2
when conventional ozonation and the AOP were com-
pared. This must be considered if reactions of molecular
O3 as well as ·OH oxidation are required.
Figure 3 shows the first-order kinetic representation of
O3 decay in both waters. During conventional ozonation
of the groundwater, an initial rapid consumption of O3
occurred, followed by slower kinetics that can be fitted
with first-order kinetics. This behavior is well-known for
conventional ozonation of natural waters (Elovitz & von
Gunten, 1999; Hoigné & Bader, 1979; Hoigné & Bader
1994). In the experiment with surface water, in which very
fast decay of O3 was observed, these two phases could not
be distinguished, because of the insufficient time resolution
of the initial phase. In contrast, during the O3/H2O2
process, only one stage could be observed in both waters.
This is because of the control of O3 decomposition by
HO2– initiation (especially in the groundwater). The cal-
culated values for the first-order rate constants (k) are
given in Table 1. Compared with conventional ozonation,
the groundwater k increases by a factor of 10 (from 1.5
3 10–4 s–1 to 1.4 3 10–3 s–1), whereas the surface water k
increases only by a factor of approximately 2 (from 2.5
3 10–3 s–1 to 5.8 3 10–3 s–1). This shows the relative impor-
tance of initiation versus promotion.
Oxidation capacity. The addition of H2O2 to an ozona-
tion process leads to a shift in the mechanism that initiates
O3 decomposition (see the introductory material). In addi-
tion, the ·OH oxidation capacity (measured by the relative
elimination of a probe compound, which only reacts with
·OH) during the oxidation process may change. Figure 4

cluded that an acceleration of O3 decomposition with an shows the influence of water type (alkalinity and NOM)
AOP is best achieved in natural waters with a low DOC on the ·OH oxidation capacity for the two waters exposed
concentration and high alkalinity. to conventional ozonation and the AOP.

©2001 American Water Works Association

ACERO ET AL | PEER-REVIEWED | JOURNAL AWWA | OCTOBER 2001 95

TABLE 3 Effect of variations in DOC on O3 decomposition kinetics, O3 exposure,
relative elimination of pCBA, and Rct
[H2O2]0 ⌬H2O2 k (k sec)‡ 冕 [O3]dt
M µM s–1 M·s
DOC = 1 mg/L
0 6.2 X 10 –4 6.3 X 10 –4
(1.7 X 10–4)
7.0 X 10–6 3.0 2.2 X 10–3 5.9 X 10–3
DOC = 2.2 mg/L
0 3.7 X 10–3 8.3 X 10–3
(1.0 X 10–3)
–6 –3 –3
7.0 X 10 1.3 4.4 X 10 2.7 X 10
*DOC—dissolved organic carbon, O3—ozone, pCBA—p-chlorobenzoic acid
†Experimental conditions were as follows: groundwater (alkalinity 5.2 mM), pH = 7.2, temperature =
o –5
11 C, [O3]0 = 1.5 X 10 M, [pCBA]0 = 0.25 µM.
‡k sec—first-order rate constant for O3 decay during the secondary phase of the reaction
§ Rct sec—Rct-value during the secondary phase of the reaction
Groundwater. The addition of H2O2 (AOP) consid-
erably enhanced the · OH oxidation capacity in the
groundwater because O3 was transformed into ·OH pri-
marily during the initiation reaction with H2O2 (values for
the final elimination of pCBA are listed in Table 1). This
is because of the different yield of ·OH formation from O3
decomposition during the initiation (Staehelin & Hoigné,
1982). During conventional ozonation in pure water in
which OH– initiation is predominant, two ·OH are formed
per three molecules of O3 decomposed. In contrast, in
the O3/H2O2 process (HO2– initiation), one ·OH is formed
per molecule of O3 decomposed. Therefore, the produc-
tion of ·OH in conventional ozonation is only two thirds
of the production in the O3/H2O2 process during the ini-
tiation. In a real water, the yield of ·OH from O3 is closer
to 0.5. Regardless, the difference between O 3 and
O3/H2O2 is still significant. The ·OH oxidation capacity
decreases from 66% pCBA elimination during the AOP
to 44% during conventional ozonation. Using a typical
HRT of 15 min in a full-scale O3 reactor, the ·OH oxi-
dation capacity increases from 23 to 54% if conventional
ozonation is changed to the O3/H2O2 process (Figure 4).
·
This significantly higher OH oxidation capacity con-
firms the efficiency of the O3/H2O2 process in eliminat-
ing micropollutants from low-DOC waters.
Surface water. In the surface water with the higher
NOM content, the ·OH oxidation capacity was compa-
rable for both conventional ozonation and the O3/H2O2
process (Figure 4, Table 1). In this water, the ozonation
process was dominated by the promoting effect of the
organic matter, where one ·OH is formed per molecule of
O3 decomposed. This theoretical ·OH/O3 yield is the
same as that for the O3/H2O2 process. Therefore, the
·OH oxidation capacity does not change significantly
with the addition of H2O2. After an HRT of 15 min, the
oxidation of an O 3 -resistant micropollutant can be
expected to be similar for both processes (Figure 4).
In comparing the groundwater and the surface water,
©2001 American Water Works Association
96 OCTOBER 2001 | JOURNAL AWWA | PEER-REVIEWED | ACERO ET AL
Figure 4 also shows that a higher over-
all ·OH oxidation capacity was reached
in the groundwater. This is a conse-
quence of the difference in the overall
% Elimination ·OH scavenging rate (scavenging rate:
pCBA Rct (Rct sec)§
k·OH,DOC[DOC] + k·OH,HCO3– [HCO3–
] + k·OH,CO32– [CO32–]; k·OH,DOC = 2.5
38 7.7 X 10 –9
3 10 4 mg–1 s–1 L (Hoigné, 1998),
(1.6 X 10–9)
k·OH,HCO3 – = 8.5 3 106 M–1 s–1,
46 1.9 X 10–8
k·OH,CO32– = 3.9 3 108 M–1 s–1) (Buxton
et al, 1988). The overall ·OH scaveng-
22 1.2 X 10–8 ing rate in the groundwater was 6.9 3
(5.5 X 10–9) 104 s–1 and 11.2 3 104 s–1 in the surface
–8
24 2.1 X 10 water. From these values, the observed
difference (a factor of 2) between the
·OH oxidation capacity in groundwa-
ter (AOP) and surface water can be
explained.
Rct value. Figure 5 shows the rela-
tionship between ln([pCBA]/[pCBA]0) and the O3 expo-
sure. For the surface water, Rct was constant over the
entire reaction in experiments for both the O3/H2O2
process and conventional ozonation. In contrast, in the
conventional ozonation experiment with groundwater,
there were two phases in the Rct plot that corresponded
to two separate kinetic stages for the O3 decay. The ini-
tial phase shows a higher Rct than the secondary phase.
The calculated values of Rct in these experiments are
given in Table 1.
The experimental data in Figure 5 lead to a conclusion
that the ratio between ·OH and O3 exposures is constant
throughout oxidation during conventional ozonation of
natural water with high DOC concentration and in the
O3/H2O2 process. Therefore, for these conditions, Rct rep-
resents the ratio between ·OH and O3 concentrations at any
time during the reaction (Elovitz & von Gunten, 1999). In
the groundwater, even in the absence of H2O2, a linear
interpretation of Rct for both stages provides an extremely
useful tool for calculating ·OH concentrations from known
O3 measurements (see “Significance for water treatment”).
During drinking water treatment, a higher ratio of ·OH
and O3 concentrations means a higher oxidation level of
O3-resistant compounds. However, the resulting smaller O3
exposure means a decrease in the O3 oxidation capacity
and less disinfection.
Influence of H2O2 concentration on the ratio H2O2/O3.
Because the addition of H2O2 ozonation had a greater
effect in groundwater than in surface water, experiments
were performed using varying H2O2/O3 ratios in the
groundwater. The initial and final H2O2 concentrations
([H2O2]0 and [H2O2]F) for these experiments are given in
Table 2 together with the calculated values for the first-
order rate constant (k), the O3 exposure (冕[O3]dt), percent
elimination of pCBA, and the Rct. O3 decomposition fol-
lowed first-order kinetics during the entire reaction when
there was a residual H2O2 concentration at the end of
the experiment. In an experiment with 0.19 g H2O2/g
O3, the final concentration of H2O2 was very small, and
the O3 decomposition mechanism changed during the FIGURE 7 Relative decrease in pCBA as a function of the
reaction time during conventional ozonation (O3) and
reaction (second stage after 25 min). the O3/H2O2 process for a groundwater with varying
The data in Table 2 show that an increase in H2O2 concentrations of DOC (1 and 2.2 mg/L)
concentration above a certain value does not improve the
·OH oxidation capacity, represented by the relative elim-
1.0
ination of pCBA. Similar results were found by Karimi et
al (1997) during trichloroethylene (TCE) and tetra-
chloroethylene (PCE) elimination in full-scale reactors, in
which the optimal ratio appeared to lie between 0.5 and 0.9
0.6 (w/w). The H2O2/O3 ratio corresponding to a stoi-
chiometric HO2–-initiated O3 decomposition is 0.35 (w/w)

Relative Decrease of pCBA

or 0.5 (mol/mol). In the examples shown in Table 2, the O3, DOC 2.2 mg/L
best improvement in micropollutant elimination was 0.8
achieved for the smallest addition of H2O2. Only a small
additional improvement could be achieved by further AOP, DOC 2.2 mg/L
increasing the H2O2 concentration. This again shows that
O3, DOC 1 mg/L
the O3 decomposition in this groundwater (low DOC and 0.7

high alkalinity) was initiation-controlled and could be

altered significantly by adding H2O2. The optimal value
depends on the relative contribution of initiation and pro-
0.6
motion steps to the overall process and should be deter- 4h
AOP, DOC 1 mg/L
mined experimentally for each raw water (Acero & von
Gunten, 2000). The O3 decomposition rate (Table 2)
depends on the absolute H2O2 concentration rather than
0.5
on the H2O2/O3 ratio because of the reaction between 0 20 40 60
O3 and HO2–. The absolute H2O2 concentration is impor- Reaction Time—min
tant to guarantee a complete O3 decomposition (see k o
Experimental conditions—pH = 7.2, temperature = 11 C, [O3 ]0 =
values in Table 2) and therefore maximum probe-com- –5 –6
1.5 ✕ 10 M, [H2O2 ]0 = 7.0 ✕ 10 M, [pCBA]0 = 0.25 µM
pound degradation within a certain HRT. According to the AOP—advanced oxidation process, DOC—dissolved organic
authors’ results and considering a reactor with an HRT of carbon, H2O2—hydrogen peroxide, O3—ozone, pCBA—
p-chlorobenzoic acid
15 min, the residual O3 concentration varied from 2.1 3
10–5 M (1.0 mg/L) for conventional ozonation to 1.8 3
10–6 M (0.09 mg/L) with an [H2O2]0 = 2.2 3 10–5 M. The
冢 冣 冢冕 [O ]dt冣 (k
t
[P]
corresponding degradation of pCBA was 15% and 75% ln ᎏᎏt = – 3 ·OH Rct + kO3) (7)
[P]0 o
for conventional ozonation and the AOP, respectively.
The increase in Rct with increasing H2O2 concentration in which k·OH and kO3 are the second-order rate con-
(Table 2) illustrates the acceleration of O3 transformation stants for the reactions of micropollutant P with ·OH
into ·OH. For small residual concentrations of H2O2, two and O3, respectively.
Rct values were observed. Similar results were obtained in The elimination of TCE for varying H2O2/O3 ratios has
experiments with synthetic waters (Acero & von Gunten, been calculated from Eq 7, with the values of O3 exposure
1998). In those experiments, the Rct was constant over and Rct given in Table 2. TCE reacts moderately with O3
the entire reaction as long as there was a significant resid- (kO3 = 17 M–1 s–1) (Hoigné & Bader, 1983a) and quickly
ual concentration of H2O2 at the end of the experiment. with ·OH (k·OH = 4.2 3 109 M–1 s–1) (Buxton et al, 1988).
Micropollutant elimination. For a batch or plug-flow For complete O3 decomposition in the absence of H2O2,
reactor, the elimination of a micropollutant (P) that reacts complete elimination of TCE is reached as a result of its
with both O3 and ·OH can be predicted by second-order reactivity with O3 and the high O3 exposure. When the
kinetics. The elimination of P is given by: H2O2/O3 ratio (w/w) is increased from 0.19 to 0.34, the
elimination of TCE decreases from 86 to 75%. With a
d[P]
– ᎏᎏ = k·OH [·OH] [P] +kO3 [O3][P] (5) higher H2O2/O3 ratio (0.7), the oxidation of TCE does not
dt
change (74%) because the process is controlled by ·OH
reactions (small O3 exposure). From these calculations, the
= k·OH Rct [O3][P] + kO3[O3][P] (6) authors concluded that the optimal H2O2/O3 ratio for
the oxidation of a moderately or highly O3-reactive
Integrating Eq 6 results in: micropollutant is given by a combination of a high O3
exposure and a minimum Rct value.

©2001 American Water Works Association

ACERO ET AL | PEER-REVIEWED | JOURNAL AWWA | OCTOBER 2001 97
 by only a factor of 2 from the low- to the high-DOC
FIGURE 8 Representation for Rct-value calculation for a
groundwater with varying DOC concentrations water because of the large contribution of the HO2–-ini-
(1 and 2.2 mg/L) tiation step for O3 decomposition. In other words, in the
presence of H2O2, O3 decomposition is largely controlled
00 by HO2–-initiation, the relative importance of the NOM
being not as significant as in conventional ozonation.
A higher DOC content also leads to a higher overall
–0.1
–0.1
OO3,3,DOC
DOC11mg/L
mg/L ·OH scavenging rate. A factor of 1.5 (from 6.9 3 104 s–1 to

RRctct==1.6
–9–9
1.6✕✕10
10 9.9 3 104 s–1) can be calculated between the water with 1
–0.2
–0.2
mg/L DOC and the water with 2.2 mg/L DOC; therefore,
a lower ·OH oxidation capacity may be expected. When
the DOC of the water increased from 1 to 2.2 mg/L, the
In([pCBA]/[pCBA] 0))
In([pCBA]/[pCBA] 0

–0.3
–0.3 OO3,3,DOC
DOC2.2
2.2mg/L
mg/L ·OH oxidation capacity decreased from 38 to 22% and
–9–9
RRctct==5.5
5.5✕✕10
10 from 46 to 24% elimination of pCBA during conventional
ozonation and the AOP, respectively (Table 3 and Figure
–0.4
–0.4 7). This decrease in the ·OH oxidation capacity by a fac-
AOP,
AOP,DOC
DOC2.2
2.2mg/L
mg/L tor of 1.7 and 1.9 for O3 and O3/H2O2, respectively, can
RRctct==–2.1
–2.1✕✕10
10
–8–8
be explained by the increase in the overall ·OH scaveng-
–0.5
–0.5
ing rate (a factor of 1.5) together with higher direct O3 con-
sumption in the higher-DOC water, which could have a
–0.6
–0.6 AOP,
AOP,DOC
DOC11mg/L
mg/L similar effect. Figure 7 also shows that for the high DOC
RRctct==1.9
1.9✕✕10
10
–8–8 concentration, the overall oxidation capacity is nearly
independent of the process (ozonation versus O3/H2O2),
–0.7
–0.7 whereas for the low DOC concentration, the overall oxi-
00 0.01
0.01 0.02
0.02 0.03
0.03
dation capacity is somewhat higher for the AOP. This is
Exposure—M.s.s
OO3 3Exposure—M
again because of the importance of the initiation reaction
Data
Datafor forconventional
conventionalozonation
ozonation(O (O3)3)and
andthe theOO3 /H 2O
3 /H 2 2process
2O processare
o o
are for O3 decomposition (discussed earlier). The differences
shown.
shown.Experimental
Experimentalconditions—pH
conditions—pH==7.2, 7.2,temperature
temperature==11 11C,
C,
[O
[O3]30]0==1.5
1.5✕✕10
–5–5
10 MM, ,[H
[H2O 2]20]0==7.0
7.0✕✕10
–6–6
10 MM, ,[pCBA]
[pCBA]0 0==0.25
0.25µµMM in the ·OH oxidation capacity in these experiments are
2O
AOP—advanced
AOP—advancedoxidation oxidationprocess,
process,DOC—dissolved
DOC—dissolvedorganic organic smaller than those in the experiments with the same
carbon,
carbon,HH2O 2—hydrogen
2O 2—hydrogenperoxide,
peroxide,OO3—ozone,
3—ozone,pCBA— pCBA—
pp-chlorobenzoic
-chlorobenzoicacid acid groundwater because of the lower O3 dose (Table 1).
The Rct was higher in the water with high DOC because
of the smaller O3 exposure (faster O3 decomposition),
Effect of seasonal variations. The groundwater used in although the ·OH exposure was also smaller (Figure 8
these experiments originates from a karstic system and and Table 3). However, when the O3/H2O2 process was
has a highly variable DOC concentration (0.9–5 mg/L) applied, the Rct values were similar in both experiments.
as a result of sudden influences of surface water infiltra- When compared with the conventional ozonation process,
tion when it rains. However, alkalinity (5.2 mM bicar- the presence of H2O2 (AOP) dominates the process in
bonate) and pH (7.2) are constant even during rain. To terms of initiating O3 decomposition. The DOC of the
study the effect of sudden changes in DOC concentration groundwater does not seem to have a strong promoting
on conventional ozonation and the O3/H2O2 process, character. Therefore, the dominance of the initiation step
experiments were performed for a typical (nonrain-influ- on the overall process can lead to a similar yield of ·OH for-
enced) DOC concentration of 1 mg/L and a higher DOC mation from O3 decomposition (similar Rct) when waters
concentration of 2.2 mg/L, which was observed after rain with different DOC concentrations are treated.
([O3] 1.5 3 10–5 M [0.7 mg/L], 0.34 g H2O2/g O3, pH Significance for water treatment. When the Rct value
7.2). Figure 6 shows the corresponding derived first-order remains constant during the entire reaction (if two linear
rate plots for O3 depletion (Table 3). A significantly higher stages are considered, there are two Rct values), it repre-
O3 decay rate can be observed in the water with the higher sents the ratio of ·OH and O3 concentrations. The exper-
DOC concentration as a consequence of an accelerated O3 imentally determined rate constants for O3 decomposition
decay because of the promoting character of the NOM. (k) and the Rct value make it possible to calculate O3 and
This is also reflected by the lower consumption of H2O2 ·OH concentrations during ozonation. With these oxi-

during the AOP (Table 3). The first-order rate constant
increased sixfold during conventional ozonation (sec-
ondary reaction stage), which is where a shift in O3 decom-
position from initiation to promotion can be observed
when the DOC increased from 1 to 2.2 mg/L. For the
O3/H2O2 process, the first-order rate constant increased
dant concentrations, the oxidation of a micropollutant can
be calculated by applying Eq 7 if the rate constant of a
micropollutant (e.g., pesticides, chlorinated solvents,
methylated benzenes, and so forth) is known for its reac-
tion with O3 and ·OH. Therefore, the authors’ kinetic
approach, which is based on an experimental calibration

©2001 American Water Works Association

98 OCTOBER 2001 | JOURNAL AWWA | PEER-REVIEWED | ACERO ET AL
of the process, avoids model calculations that are based FIGURE 9 Atrazine degradation as a function of the reaction time
on complicated O3 decomposition mechanisms for a com- for conventional ozonation (O3) and the O3/H2O2
plex natural water matrix with many unknown reactions. process
This kinetic approach was tested by comparing the
Ozonation experiment
measured and calculated elimination of a micropollutant. AOP experiment
Atrazine was added to the groundwater and surface water Model calculations
0.25
as a micropollutant, and its elimination was followed
with the reaction time. Figure 9 shows the experimental
results (symbols) and model calculations (lines) for
atrazine oxidation in the groundwater during conven-
tional ozonation and O3/H2O2 treatment. The decrease in 0.20

atrazine was estimated by calculating the O3 concentra-

tion using a first-order approximation (k) and the ·OH

Atrazine—µM
concentration with the Rct and combining it with the
atrazine kinetics using a simple spreadsheet calculation. 0.15
Ozonation:
An O3 dose of 2.3 3 10–5 M (1.1 mg/L) and 0.34 gH2O2/g 65% O3 degradation
35% OH degradation
O3 was applied at pH 7.2. The experimental results for
the O3 depletion rate and Rct value are given in Table 2.
The rate constants for the reaction of atrazine with O3 and 0.10
·OH were 4 M–1 s–1 and 3 3 109 M–1 s–1, respectively,
AOP:
under the experimental conditions applied (11oC) (Acero 7% O3 degradation
93% OH degradation
et al, 2000). The good agreement between model calcu-
lations and experimental results in Figure 9 supports the 0.05
authors’ kinetic formulation to predict micropollutant 0 100 200 300

degradation. During conventional ozonation of ground- Reaction Time—min

water, O3 is relatively stable, and O3 exposure is conse-
quently high. Therefore, most of the atrazine is degraded
by reaction with molecular O3 (65%). In contrast, for
the O3/H2O2 process, the O3 pathway is not very signif-
icant (7% O3 degradation) because of the fast transfor-
mation of O3 into ·OH, even at pH 7.2.
Data are shown for a groundwater (DOC 0.9 mg/L, alkalinity 5.2
m M). Symbols represent experimental data, and lines represent
model calculations. Experimental conditions—pH = 7.2,
o –5 –5
temperature = 11 C, [O3 ]0 = 2.3 ✕ 10 M, [H2O2]0 = 1.1 ✕ 10 M,
[pCBA]0 = 0.25 µM, [Atrazine]0 = 0.25 µM
AOP—advanced oxidation process, DOC—dissolved organic
carbon, H2O2—hydrogen peroxide, O3—ozone, pCBA—
p-chlorobenzoic acid

The kinetic formulation presented here allows the cal-

culation of micropollutant elimination as well as the for-
mation and further degradation of metabolites. By com-
bining kinetic parameters (rate constant for reaction with
O3 and ·OH for each metabolite and the proportion of by-
products formed from each metabolite) with the O3 and
·OH concentrations, the evolution of metabolite concen-
trations can be predicted for ozonation processes (Acero
et al, 2000).
CONCLUSIONS
The efficiency of conventional ozonation and the
O3/H2O2 process with respect to oxidation of O3-resistant
micropollutants strongly depends on the water matrix.
alkalinity, i.e., O3 decomposition is controlled by initia-
tion). This is mainly because of a higher ·OH yield if
HO2– is the main initiator.
• Similar to conventional ozonation, the AOP
O3/H2O2 can be characterized by a constant ratio (Rct) of
·OH and O concentrations, which varies for the two
3
waters in this study between 5 3 10–9 and 3.5 3 10–8. Cal-
ibration of a water with respect to the Rct makes it pos-
sible to predict the degree of oxidation of any micro-
pollutant during any O 3 /H 2 O 2 process if the
corresponding rate constants for the reactions with O3 and
·OH are known.

• For a given O3 dose, the relative oxidative removal
of a micropollutant is controlled by the overall scaveng-
ing of the water matrix, which is dominated by NOM,
carbonate, and bicarbonate.
• For a constant O3 dosage, the application of the
O3/H2O2 process accelerates the oxidation of an O3-resis-
tant micropollutant relative to a conventional ozonation
process. It either does not change the relative oxidative
removal (waters with high DOC concentration, i.e., high
degree of promotion) or increases the relative oxidative
removal (waters with low DOC concentration and high
• The optimal H2O2/O3 ratio is given by the mini-
mum Rct value that guarantees the maximum degree of
micropollutant oxidation. A higher H 2 O 2 /O 3 ratio
increases the Rct and accelerates the process but does not
lead to enhanced removal of micropollutants. In addi-
tion, the O3 exposure decreases, which may be undesir-
able if direct O3 reactions are important.
ACKNOWLEDGMENT
The authors acknowledge M. Elovitz for stimulating dis-
cussions and for reviewing the manuscript. J.L. Acero thanks

©2001 American Water Works Association

ACERO ET AL | PEER-REVIEWED | JOURNAL AWWA | OCTOBER 2001 99
the Ministerio de Educación y Ciencia of Spain for provid-
ing funds (FPI Grant) necessary to perform this research.
ABOUT THE AUTHORS:
Juan L. Acero is an assistant professor
at the University of Extremadura,
Departemento de Ingenieria Quimica,
Badajoz, Spain; e-mail
<jlacero@unex.es>. He earned his BS
degree and PhD from the University of
Extremadura. Urs von Gunten* is a
senior scientist and the head of the Department for Water
Resources and Drinking Water at the Swiss Federal Insti-
tute for Environmental Science and Technology,
EAWAG, Ueberland Strasse 133, POB 611, CH-8600,
Duebendorf, Switzerland; e-mail <vongunte@eawag.ch>.
*To whom correspondence should be addressed
If you have a comment about this article, please contact
us at <journal@awwa.org>.

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100 OCTOBER 2001 | JOURNAL AWWA | PEER-REVIEWED | ACERO ET AL