ARTICLE IN PRESS

WAT E R R E S E A R C H 40 (2006) 3695 3704

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Comparison of the efficiency of dOH radical formation

during ozonation and the advanced oxidation processes
O3/H2O2 and UV/H2O2

Erik J. Rosenfeldta,b, Karl G. Lindenb, Silvio Canonicaa, Urs von Guntena,

a
Swiss Federal Institute of Aquatic Science and Technology, Eawag, 8600 Dubendorf, Switzerland
b
Department of Civil and Environmental Engineering, Duke University, Durham, NC 27708-0287, USA

art i cle info A B S T R A C T

Article history: Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and
Received 6 June 2006 chemical differences in the fundamental processes used to produce dOH radicals. This
Received in revised form study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV
4 September 2006 (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce dOH
Accepted 12 September 2006 radicals. Bench scale dOH radical formation data was generated for each AOP using para-
Available online 31 October 2006 chlorobenzoic acid (pCBA) as an d
OH radical probe compound in three waters, Lake
Keywords: Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs
Advanced oxidation were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the
d
OH radical addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption
Ozone over the ozone only process. Interestingly, the relatively high UV/AOP operational costs
O3/H2O2 were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the
UV/H2O2 UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was
always less than the ozone energy cost. As the dOH radical exposure increased, the energy
gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some
water quality scenarios.
& 2006 Elsevier Ltd. All rights reserved.

1. Introduction During ozonation, organic contaminants are oxidized in

Advanced oxidation processes (AOPs) have been defined as the
aqueous phase chemical oxidation of target organic or inorganic
pollutants by a process involving hydroxyl free radicals (Singer
and Reckhow, 1999). Hydroxyl radical (dOH) reacts very quickly
with many organic species, displaying kinetic constants in the
range from 108 to 1010 M
1 s
1 (Haag and Yao, 1992). AOPs can be
generated via a number of aqueous treatment scenarios
including ozone, ozone/H2O2, UV/ozone, UV/H2O2, UV/H2O2/O3,
Fentons processes, and photocatalysis. Previous reviews de-
scribe these AOPs, including ozone-based (von Gunten, 2003a)
and UV- based (Legrini et al., 1993) processes.
two ways. Ozone itself can directly react with dissolved
chemicals, at varying rates, and is a highly selective
oxidant (Hoigne and Bader, 1983a, b; Hoigne et al., 1985).
In addition to direct oxidation, ozone decomposes via a
chain reaction mechanism to form dOH radicals, which in
turn can oxidize the pollutant (Hoigne, 1982). The two
pathways can lead to different products and display different
transformation kinetics (von Gunten, 2003a). When hydrogen
peroxide is added to the ozone system, the decomposition of
O3 into dOH radicals is accelerated, essentially shifting
the process entirely to an AOP. This is recommended for
waters in which ozone is stable and resulting pollutant

Corresponding author. Tel.: +41 44 823 5270; fax: +41 44 823 5210.
E-mail address: vongunten@eawag.ch (U. von Gunten).
0043-1354/$ - see front matter & 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2006.09.008
 ARTICLE IN PRESS
3696 WAT E R R E S E A R C H
Nomenclature
AOP advanced oxidation process
CO3 ;i initial ozone concentration (mg L
1)
[CO2
3 ] concentration of carbonate in water
DOC dissolved organic carbon (mg L
1)
E0 a
average UV fluence rate (mW L
1)
E0 a(l) wavelength specific average fluence rate in the
reactor (mW L
1)
E$ local cost of electricity ($ kWh
1)
EH2 O2 hydrogen peroxide energy requirement (kWh L
1)
E0 lamp(l) wavelength specific fluence rate at the surface
of the lamp (mW L
1)
EEO electrical efficiency per order
EO3 energy of the ozone process (kWh L
1)
[HCO
]
3 concentration of bicarbonate in water
H0 UV fluence (mJ L
1)
H$ local cost of hydrogen peroxide ($ kg
1 H2O2)
H2O2 hydrogen peroxide
HPLC high performance liquid chromatography
k0 D
d observed fluence based pCBA direct photolysis
pseudo-first order rate constant (L mJ
1)
kd0
direct photolysis time based pseudo-first order
rate constant (s
1)
k0 obs observed pseudo-first order rate constant for
pCBA oxidation (s
1)
k0 D
obs observed pseudo-first order fluence based rate
constant for pCBA oxidation (L mJ
1)
degradation is slow (Acero and von Gunten, 2001; Griffini and
Iozzelli, 1996).
UV-based AOPs also transform pollutants in two ways.
Some organic chemicals absorb UV light directly, and
absorption of this high-energy radiation can cause destruc-
tion of chemical bonds and subsequent breakdown of the
contaminant (Schwarzenbach et al., 2003). However, some
organic species do not degrade very quickly or efficiently by
direct UV photolysis. Therefore, addition of H2O2 to the UV
process creates AOP conditions, often increasing the rate of
contaminant degradation significantly. H2O2 absorbs UV light,
and breaks down into dOH radicals (Bolton and Cater, 1994),
degrading the contaminant via dOH radical oxidation. The
quantum yield for the process is 1 mol dOH per Einstein
absorbed by H2O2.
There has been little research comparing AOPs for their
potential to form dOH radicals. Several attempts to compare
different AOPs for their effectiveness at destroying target
pollutants include Muller and Jekel (2001), Muller et al. (2001)
who used the concept of EEO put forth by Bolton and Bircher
(1996) to compare the electrical energy needed to degrade
atrazine by one order of magnitude via the UV/H2O2, UV/O3,
and O3/H2O2 processes. The results of these studies indicated
that for Berlin tap water and a model water, the ozone based
processes were an order of magnitude more energy efficient
than the UV based processes. However, these results were
dependent upon reactor geometry and upon the specific
40 (2006) 3695 3704
kOH,N second order rate constant for the reaction of dOH
radicals with species N (M
1 s
1)
LP low pressure mercury vapor UV lamp
MP medium pressure mercury vapor UV lamp
ZUV UV lamp efficiency (30% for LP, 15% for MP (USEPA,
2003))
OH
d
hydroxyl radical
[RdOH] concentration of dOH radical (M)
OHdt dOH radical exposure (M s)
O3 ozone
pCBA para-chlorobenzoic acid
%dOHpCBA percent of dOH radical available for oxidation
of pCBA in ozone or UV/H2O2 experiments
Rct ratio of dOH radical exposure to ozone exposure
in ozone processes
RF reflection factor of air/quartz/water interface
ROH,UV dOH radical exposure per UV fluence in the UV/
H2O2 AOP (M s L mJ
1)
[S] concentration of scavengers in water (M)
t time (s)
Ufluence UV lamp energy requirement for a given fluence
(kWh L
1)
UV ultraviolet
WF water factor used to calculate the average fluence
rate from the incident fluence rate WF 1

e
2:303alb =2:303alb (Bolton and Stefan, 2002)
a(l) wavelength specific UV energy absorbance (cm
1)
b reactor pathlength (cm)
water being treated. Therefore, the comparison between the
technologies could not be generalized, and was not applicable
to different water matrices. Bolton and Cater (1994) indicated
that under optimum conditions, the energy required to
produce one mole of dOH radicals by the UV/H2O2 process
was 0.54 kWh as opposed to the 1.05 kWh needed to create
one mole by the ozone/peroxide process. They also deter-
mined that the comparative efficiency is dependent upon UV
absorbance of the water, and in waters with high UV
absorbance, the UV process can become more energy
consumptive than the ozone process.
The amount of dOH radical produced and a fraction thereof
used for targeted oxidation for each process are important
comparative parameters for evaluation of different AOPs. The
goal of this study was to directly compare the energy of dOH
radical oxidation by ozone, ozone/H2O2, low-pressure (LP) UV/
H2O2, and medium pressure (MP) UV/H2O2. To address this
goal, ozone and UV/H2O2 bench scale experiments were
performed, examining the degradation of a commonly
utilized dOH radical probe compound, para-chlorobenzoic
acid (pCBA) (Elovitz and von Gunten, 1999, 2000; Pines and
Reckhow, 2003; Han et al., 2002; Acero et al., 2003), in three
distinct waters.
Rct, defined as the steady state ratio of dOH radical exposure
to O3 exposure was determined by pCBA as the probe
compound for dOH radical exposure. pCBA is an ideal probe
compound for ozone AOP studies because it displays slow
 ARTICLE IN PRESS
WAT E R R E S E A R C H
reaction rates with ozone (kO3o1 M
1 s
1), but rapid oxidation
kinetics with the dOH radical (kOH,pCBA 5  109 M
1 s
1)
(Elovitz and von Gunten, 1999). pCBA is also an ideal probe
compound for UV AOP studies for similar reasons. The
quantum yield of pCBA was determined to be 0.026 using
UV light in the wavelength range of 250350 nm (Chen et al.,
1998), indicating that direct photolysis of pCBA will likely be
slow compared to the advanced oxidation pathway.
Utilizing this approach, the energy for dOH radical oxidation
between AOPs was compared, independent of reaction time
and reactor geometry, but accounting for water matrix
properties.
2. Materials and methods
2.1. Reagents and waters
All chemicals for these experiments were purchased from
Fluka (Buchs, Switzerland) or Merck (Darmstadt, Germany),
with the exception of the Indigo trisulfonate potassium salt,
which was obtained from Riedel-de Haen (Hanover, Ger-
many). HPLC reagent grade methanol was from Scharlau
Chemie S.A. (Barcelona, Spain).
Pure water was obtained from a Millipore Quantum EX
system with Ultrapure Organex Cartridge and Q-Guard 2
cartridges, and a Millipore 0.22 micron Millipak Express filter
(Billerica, MA). The experimental waters were collected raw
from Lake Greifensee and Lake Zurich in Switzerland.
Additionally, Lake Zurich water was spiked with NaHCO3 to
increase alkalinity to a concentration of approximately 8 mM
(Table 1). Natural waters were filtered with a 0.45 mm filter, and
stored at 4 1C in glass containers prior to use. Water quality
parameters (alkalinity, DOC, and nitrate) were determined
using standard methods (APHA, AWWA and WEF, 2000). Table
1 displays the water quality parameter measurements.
Ozone was generated in a Fischer Model 502 Ozon-
Generator (Germany), with direct O2 feed from Carbagas
(Bern, Switzerland). The ozone-enriched oxygen gas was
bubbled into one liter of water on ice to create an approxi-
mately 1 mM saturated ozone stock solution. The concentra-
tion of the ozone stock solution was determined via UV
absorbance at 258 nm (e258 3000 M
1 cm
1).
2.2. Analytical methods
A Cary 100 Bio UVvis spectrophotometer (VarianPalo Alto,
CA), and a UVIKON 940 spectrophotometer (Kontron Instru-
ments, Watford, UK) were used to measure UV absorption.
Table 1 Water quality of the waters examined in this study
Water pH DOC (mg L
1) Alkalinity (mM as HCO

Lake Greifensee 8.0 3.5
Lake Zurich 7.9 1.4
Lake Zurich+alkalinity 8.2 1.3
4 0 (200 6) 369 5 370 4 3697
The indigo method (Hoigne and Bader, 1981) was used for
ozone residual analysis, and the I
3 method (Klassen et al.,
1994) was used to measure residual H2O2.
Atrazine and pCBA were detected using a Hewlett-Packard
Series 1050 HPLC with UV/vis detection. A Macherey-Nagel
CC125/4 Nucleosil 100-5 C-18 column was used for pCBA
detection, and a Hewlett Packard LichroCART 250-4 reverse
phase C-18 column (5 mm) for atrazine separation. An eluent
consisting of 60%:40% methanol: H2O (adjusted to pH 2 with
H3PO4) was used for pCBA and 50:50 methanol:H2O was used
for atrazine. UV absorbance at 240 and 220 nm was used for
pCBA and atrazine measurement, respectively. Quantification
limits of 0.05 mM for pCBA and atrazine were achieved.
2.3. Experimental setup
Two ozone experimental setups were employed. To determine
the Rct in Lake Greifensee water and Lake Zurich water,
dynamic experiments were performed in a 500 mL batch
reactor spiked to the following final concentrations: 5 mM
borate (pH 8 experiments) or phosphate buffer (pH 6.5
experiments), and 0.5 mM pCBA. The solution was kept at
15 1C and pH was adjusted using 1 M HCl or 1 M NaOH. Ozone
stock solution was added to the proper concentration (62.5 mM
in Lake Greifensee water, and 20.8 mM in Lake Zurich waters)
via an inlet tube, and samples were taken at time predeter-
mined intervals for ozone and pCBA analysis. For ozone
dosage experiments, a vial was filled with the water to be
tested, and then spiked to achieve the buffer and pCBA
concentrations above. The solution was kept at 15 1C and pH
was adjusted using 1 M HCl or 1 M NaOH. Ozone stock was
added at the proper concentration (2.08, 4.17, 10.4, 20.8, and
104 mM O3) at time zero. Samples were quenched with Na2SO3
after 30 min and 15 h for pCBA analysis via HPLC. Ozone/H2O2
experiments were performed exactly as the ozone experi-
ments with the addition of H2O2 (1:2 or 1:1 on a molar basis
H2O2:O3 ratio) to the reaction mixture before the addition of
ozone.
UV experiments were performed in a DEMA model 125
merry-go-round photoreactor (Hans Mangels GmbH, Born-
heim-Roisdorf, Germany), equipped with either a 15 W
Heraeus Noblelight TNN 15/32 low pressure mercury vapor
lamp (Hanau, Germany), or a 150 W Heraeus Noblelight TQ
150 medium pressure mercury lamp (Hanau, Germany)
surrounded by two square mesh stainless steel wire cloths,
open area 53% and 40%, respectively, resulting in approxi-
mately 21% light transmission. Reactor rotation and time was
begun upon placement of the sample-filled, UV transparent

2
3 /CO3 ) Nitrate (mg N L
1) UV 254 (cm
1)
3.4 1.6 0.067
2.7 0.8 0.032
8.2 0.8 0.036
 ARTICLE IN PRESS
3698 WAT E R R E S E A R C H 40 (2006) 3695 3704

quartz tubes. At the predetermined irradiation time to
achieve a target fluence, a tube was removed for pCBA and
H2O2 analysis.
The UV experiments were performed in three stages. First,
atrazine actinometry experiments were performed to deter-
mine the irradiance incident to the surface of the tube for
each lamp. Once this irradiance was determined, direct UV
experiments were run without the addition of H2O2 to
determine the rate of direct photolysis of pCBA. Finally, UV/
H2O2 experiments were performed to determine oxidation of
pCBA by UV in combination with H2O2 concentrations of 2, 10,
and 50 mg L
1.
2.4. Atrazine actinometry for UV fluence calculation
Atrazine actinometry experiments were performed to deter-
mine the fluence rate in the quartz tube for each lamp at the
limit of negligible optical density. Next, the average UV
fluence rate (mW L
1) in the completely mixed sample was
determined using an integrated form of the Beer-Lambert law
including UV absorbance, and sample depth (Linden and
Darby, 1997). The UV fluence delivered to a sample was
calculated as the average UV fluence rate multiplied by the
exposure time. For the LP UV source, UV fluence was
calculated as the radiation emitted at 254 nm. For the broad-
band MP UV source, the fluence was calculated as the sum of
the total UV output in the 200300 nm region.
For experiments performed using the LP lamp, a fluence
rate of 4.55  10
9 Einstein cm
2 s
1 for 254 nm radiation was
determined by atrazine actinometry, employing a quantum
yield for atrazine depletion of 0.05 mol Einstein
1 (Beltran
et al., 1993). For the MP lamp, atrazine actinometry yielded a
fluence rate of 9.3  10
9 Einstein cm
2 s
1 for UV light in the
wavelength range of 200300 nm. The latter fluence rate was
calculated using the above quantum yield value, which
should be a good approximation for the average quantum
yield (the main spectral contribution to atrazine photolysis
with the MP lamp is given by the range of 250270 nm, which
has a wavelength-independent quantum yield (Sharpless
et al., 2003)).
and included DOC (kOH,DOC 2.5  104 L mg
1 s
1) (Larson
6
and Zepp, 1988), HCO
3 kOH;HCO3 8:5  10 M



1
1
s ,

2 8
1
1
CO3 kOH;CO
2 3:9  10 M s (Hoigne et al., 1985; Buxton
3
et al., 1988) along with incorporating the spiked pCBA
kOH,pCBA 5  109 M
1 s
1) (Elovitz and von Gunten, 1999) and
H2 O2 kOH;H2 O2 2:7  107 M
1 s
1 (Buxton et al., 1988). Percent
available dOH radical data is tabulated (Table 2) for each
process and will be utilized to aid in the discussion of
differences in the processes between water matrices. The
scavenging of dOH radicals by ozone can also be a significant
sink for dOH radicals. However, the kinetics of the reaction
between ozone and dOH radicals are not well defined, and a
sensitivity analysis showed that for most of the conditions
tested in this study, inclusion of this parameter resulted in
less than a 0.5% difference in %OHpCBA . Rather than to include
the significantly variable kOH,O3 rate constant, which has been
measured between 108 M
1 s
1 to 2  109 M
1 s
1 (von Gunten,
2003a), the effect of dOH radical scavenging by ozone was
neglected in this study.
These calculated values are utilized for qualitative compar-
ison purposes only, and are presented acknowledging that
discrepancies within the reported data exists regarding reaction
rate constants, that errors in measurement of water quality
parameters can significantly alter the parameter, and that this
discussion is only valid for the initial conditions. Even with
these qualifications, the percent available dOH radical will be a
useful qualitative tool to illustrate differences between waters
and discuss underlying reasons for these differences.
3.2. Using Rct and ROH,UV to characterize the waters under
typical treatment conditions
The steady state parameters Rct and ROH,UV were utilized to
characterize ozone-based and UV/H2O2 AOPs for each water
under typical operating conditions. These typical conditions
consist of an ozone dose of 1 mg L
1 per 1 mg L
1 DOC, and LP
or MP UV+0.29 mM (10 mg L
1) H2O2. Rct is defined as the ratio
of dOH radical exposure to ozone exposure (Elovitz and von
Gunten, 1999), and ROH,UV is a new concept, defined as the
d
OH radical exposure (Ms) per UV fluence (mJ L
1). (Rosenfeldt
and Linden, 2005).

3. Results and discussion 3.2.1. Ozone processes

Bench scale testing was performed in Lake Greifensee, Lake
3.1. Theoretical efficiency of AOPs Zurich, and Lake Zurich+alkalinity waters to characterize the
waters using the Rct concept, fully developed in Elovitz and
One of the major factors governing AOPs is the fraction of dOH
radicals available for the oxidation of the target contaminant
as compared to the fraction of dOH radicals scavenged by the
Table 2 Percent OH radical available for oxidation of
background water matrix. To determine the theoretical effect
0.5 lM pCBA in water treated with ozone and
of the scavenging in each water, the percent of dOH radical UV+0.29 mM H2O2
available for oxidation of pCBA was calculated using Eq. (1).
The value considers only the theoretical ratio of the rate of
Ozone UV+0.29 mM H2O2
oxidation of pCBA as compared to the rate of oxidation of all
d
OH radical scavengers (S) in the water. Water pH 6.5 pH 8 pH 6.5 PH 8
kOH;pCBA pCBA
%OHpCBA 100 P . (1) Lake Greifensee 1.8 1.6 1.7 1.5
fkOH;pCBA pCBA kOH;S Sg Lake Zurich 3.2 2.9 2.9 2.6
The scavenging rate in the system was calculated Lake Zurich+alkalinity 1.6 1.3 1.5 1.3

from the water quality information listed in Table 1,

 ARTICLE IN PRESS
WAT E R R E S E A R C H 4 0 (200 6) 369 5 370 4 3699

von Gunten (1999). To determine the Rct, the oxidation of into one equation.
pCBA as a function of ozone exposure (M min) is measured, to   Z
pCBAo
calculate the production of hydroxyl radicals per unit ln k0d t kOH;pCBA OHdt k0obs t (3)
pCBA
consumption of ozone. Fig. 1 displays the Rct values deter-
mined in Lake Greifensee water with an ozone dose of and
R
62.5 mM, and Lake Zurich water and Lake Zurich+alkalinity OHdt
k0obs k0d kOH;pCBA . (4)
water with an ozone dose of 20.8 mM. t
The Rct values in Fig. 1 correspond well to those found by To generalize the kinetics of a UV system, it is necessary to
Elovitz and von Gunten (2000), where Rct values were reported convert time based rate constants into UV fluence based rate
for decarbonated Lake Zurich water (pH 6.5 at 15 1C) of constants (Bolton and Stefan, 2002). In this case, dividing both
1.1  10
8, and for Lake Zurich water (pH 7.8) of 1.5  10
8. sides of Eq. (4) by the volume-based UV average fluence rate,
They also agree with scavenging rates as described by the E0 a (mW L
1), converts the rate constants and results in Eq. (5).
percent of dOH radicals available for pCBA oxidation (Table 2). R
D D kOH;pCBA OH dt
First, as scavenging increases, it is expected that the fraction k0 obs
k0 d . (5)
E0a t
of dOH radicals available for oxidation of pCBA will decrease.
The Rct values in Fig. 1 agree with trends regarding the Because UV fluence (H0 ) is simply the product of average
available dOH radical after scavenging by the background fluence rate and time, upon rearrangement of Eq. (5), ROH,UV
matrix. Secondly, ozone decomposition to dOH radical is (mol mW
1) can be determined (Eq. (6)).
enhanced at high pH values (Hoigne, 1982). This enhanced R D D
OH dt k0 obs
k0 d
decomposition dominated the process at pH 8, resulting in ROH;UV . (6)
H0 kOH;pCBA
greater Rct values than at pH 6.5, despite the fact that the dOH
radical scavenging is elevated at pH 8, resulting in lower ROH,UV values for each water treated with the LP UV and MP
% OHpCBA values in Table 2. The ozone/H2O2 process displays UV+0.29 mM H2O2 AOPs are presented in Fig. 2.
the highest Rct. This is due to the enhanced initiation of the These ROH,UV values can be compared to examine the effect
ozone transformation to dOH radical by HO
2. of water quality on the dOH radical exposure by the UV/H2O2
system. In the UV/H2O2 system, three factors affect dOH
radical availability: formation rate and scavenging rate of dOH
3.2.2. The UV/H2O2 process
radical and UV absorbance of the water. By definition, ROH,UV
Bench scale testing was also performed to determine the
already contains a correction accounting for water absor-
ROH,UV for each water at 0.29 mM initial hydrogen peroxide.
bance, which leaves the formation and scavenging rates of
This new steady state parameter is analogous to Rct used for d
OH radical as the only determining factors of ROH,UV. At
ozonation, and was developed as follows. Eq. (2) is the
constant H2O2 concentration, formation rates of dOH radical
governing equation describing transformation of pCBA by
based on average fluence rate should have constant values for
the UV/H2O2 process.
LP or MP irradiation conditions and ROH,UV values should be
dpCBA
  influenced only by dOH radical scavenging kinetics. For Lake

k0d kOH;pCBA OH pCBA . (2)
dt Greifensee and Lake Zurich waters, %OHpCBA values from
Eq. (3) is the result of the integration of Eq. (2). Dividing both Table 2 correspond well with the experimental results of Fig.
sides by time results in Eq. (4), incorporating the overall 2. However, the ROH,UV values of Lake Zurich+alkalinity water
observed, direct photolysis, and dOH radical rate constants presents a more complicated picture. Even though the

5 3.9
Ozone / H O AOP
2 2
4

pH 6.5
Rct (10-8)

3 pH 8
2.0

2 1.4
1.2
1.2

1 0.69
0.64

0
Lake Greifensee Lake Zurich Lake Zurich + alkalinity

Fig. 1 Rct values for Lake Greifensee, Lake Zurich, and Lake Zurich+alkalinity waters during ozonation for all conditions
tested (95% confidence intervals). The ozone dose is 62.5 lM (Lake Greifensee water), or 20.8 lM (Lake Zurich waters), initial
pCBA is 0.5 lM.
 ARTICLE IN PRESS
3700 WAT E R R E S E A R C H 40 (2006) 3695 3704

5.0
LP UV, pH 6.5

ROH,UV (10-13 M s L mJ-1)

4.0 LP UV, pH 8
MP UV, pH 6.5

3.0 MP UV, pH 8

2.0

1.0

0.0
Lake Greifensee Lake Zurich Lake Zurich + alkalinity

Fig. 2 ROH,UV values for Lake Greifensee, Lake Zurich, and Lake Zurich+alkalinity waters for LPUV+0.29 mM H2O2, with 95%
confidence intervals.

0.5
Lake Greifensee Medium Pressure UV
Absorbance (cm-1) and Relative

Low Pressure UV Lamp Lamp Emission

Emission
0.4

0.3 Lake Zurich

Emission

+ alkalinity

0.2
Lake Zurich

0.1
0.29mMH2O2

0
200 220 240 260 280 300 320 340 360 380 400
Wavelength (nm)

Fig. 3 Background water absorbance of Lake Greifensee, Lake Zurich and Lake Zurich+alkalinity water, absorbance of
0.29 mM H2O2, and relative emission spectra (normalized to the maximum emission) for typical LP and MP UV lamps.

%OHpCBA is less than in the Lake Greifensee or Lake Zurich treated water and under the same irradiation conditions, the
water, the ROH,UV values are comparable or higher under all production rate of dOH radical for Lake Greifensee water will
tested conditions in the Lake Zurich+alkalinity water. This be reduced by a factor of E2 with respect to the same rate in
observation is magnified at lower pH, indicating that a Lake Zurich water. This means that, in terms of energy
plausible explanation of this behavior may be attributed to consumption for the production of UV light, the differences
possible presence of a transition metal impurity in the added between the waters given in Fig. 2 will be amplified by a
NaHCO3 salts, which might lead to an enhanced production of maximum factor of E2 depending on reactor geometry. The
d
OH radical (for instance through a photo-fenton type reduced effectiveness of the MP system, compared to the LP
mechanism). system, is mainly due to a smaller spectral overlap of emitted
Nevertheless, the UV absorbance of the water must be UV radiation with the absorption spectrum of hydrogen
taken into account for energy calculations presented further peroxide.
on in this paper. Absorbance varies depending on the average
path length of UV light, which is defined by the photochemi-
3.3. d
OH radical exposure for ozone doses and applied UV
cal reactor geometry. Background water absorption becomes
fluences
increasingly important at longer path lengths and its max-
imum effect is reached for total absorption of UV light by the
To provide a context for comparing the technologies, the dOH
treated water. Fig. 3 displays the relevant absorption and
radical exposure (similar to a Ct concept) for each system was
emission spectra involved and shows that UV absorbance is
determined, with the second set of ozone experiments, which
dominated by the background water absorption (mainly
measured the pCBA degradation after complete ozone con-
organic matter over the whole spectral range and nitrate
sumption. This pCBA degradation was directly related to the
below E230 nm). R 
d
OH radical exposure OH dt , using Eq. (7).
Hydrogen peroxide at the concentration levels in our study

Z
(0.29 mM) absorbs only a small fraction of the available UV ln pCBAo =pCBA
OHdt . (7)
light. In the limiting case of total UV light absorption by the kOH;pCBA
 ARTICLE IN PRESS
WAT E R R E S E A R C H
R
Fig. 4 displays OHdt as a function of initial ozone
concentration, for ozone doses of 2.08, 4.17, 10.4, 20.8, and
104 mM O3 (0.1, 0.2, 0.5, 1, 2, 5 mg L
1), in Lake Greifensee and
Lake Zurich waters at pH 6.5 and pH 8. Also displayed in Fig. 4
R E0lamp lt
is OHdt when hydrogen peroxide is added to the ozone
process in Lake Zurich water at pH 8. Although the Rct is
increased with the addition of hydrogen peroxide (shown for
Lake Zurich+alkalinity water in Fig. 2), Fig. 4 clearly displays
that there is no significant improvement in overall dOH
radical exposure with the addition of hydrogen peroxide,
consistent with the findings presented in von Gunten (2003a).
However, the faster rates of dOH formation will result in
smaller system size compared to ozone alone.
R
OHdt was also plotted as a function of UV fluence for
varying initial hydrogen peroxide concentrations, corre-
sponding to approximately 0.08, 0.29, and 1.45 mM (2, 10,
and 50 mg L
1) initial H2O2 (Fig. 5). It is important to note that
the UV fluence to achieve similar dOH radical exposures is
approximately double in the MP UV systems as compared to
the LP UV systems. This can be attributed, as discussed
earlier, to a better overlap between lamp emission spectrum
and absorption spectrum of hydrogen peroxide for the LP
systems than for the MP systems.
3.4. Energy comparison of ozone and UV processes
The theoretical electrical energy needed for ozone and UV/
H2O2 processes to yield a certain dOH exposure was calculated
and compared to evaluate the energy requirements for
formation of dOH radicals. The energy required for an ozone
exposure in a model reactor EO3 can be calculated by
multiplying the ozone close by the energy efficiency of ozone
generation (1826 kWh kg
1 USEPA, 1999).
To calculate the theoretical energy required for the UV
processes, the kWh for the fluence required to yield a certain
R
d
OH radical exposure OHdt, as well as the energy of the
hydrogen peroxide production must be considered. Once the
UV fluence level has been established, the mJ L
1 emitted
from the lamp at the surface of the quartz sleeve in a model
reactor can be calculated using the water factor (with inputs
0.0 1.0
14
OH radical exposure (1011 M min)
Lake Zurich, pH 6.5
12 Lake Zurich, pH 8
Lake Zurich, ozone + H2O2, pH 8
10 Lake Greifensee, pH 6.5
Lake Greifensee, pH 8
8
6
4
2
0
0 20
Fig. 4 OH radical exposure as a function of the ozone dose in Lake Greifensee and Lake Zurich waters, pH 6.5 and pH 8.
4 0 (200 6) 369 5 370 4 3701
of the water absorbance, and an assumed pathlength) and the
reflection factor, according to Eq. (8).
E0a lt
. (8)
RF  WF
Eq. (9) converts the quartz sleeve fluence to the energy
required by the UV lamp.
3P
00
1h 1 kW
E0lamp lt 3600 s 1106 mW
Ulamp 200 . (9)
ZUV
Another energy consideration in the UV system is the
hydrogen peroxide energy EH2 O2 . The local EH2 O2 was
calculated for four regions, California, USA average, Germany,
and France. Table 3 displays the local costs of hydrogen
peroxide (H$), electricity cost (E$), the calculated ratio of these
values for each region and the average of this ratio. The
energy requirements of the two processes are compared for
Lake Greifensee and Lake Zurich waters in Fig. 6, which
displays the ratio of the energy required for the UV processes
to that of the ozone processes.
As the dOH radical exposure increases, the energy ratio of
UV to ozone processes decreases dramatically. To increase
d
OH radical exposure with an ozone process involves
increasing the ozone dose, and therefore the ozone energy.
However, for the UV AOPs, a higher dOH radical exposure
occurs with the addition of UV fluence, which is negligible in
the peroxide energy dominated process. This results in a UV
AOP energy that is essentially constant with increasing dOH
radical exposure. In certain cases, the energy ratio can be very
close to or less than one (zero on the log scale shown in Fig. 6),
implying the UV process is near to or less energy intensive
than the ozone process. This situation occurs only at 0.1 and
0.3 mM initial peroxide concentrations and high dOH radical
exposure. Interestingly, the UV portion of the UV/H2O2 AOP
energy cost is a small fraction of the total UV/H2O2 cost. For
instance, for an dOH radical exposure of 1  10
12 M min in
Lake Greifensee water at pH 6.5, the LP UV energy is only 10%
of the total UV/H2O2 AOP (at 2 mg L
1 H2O2) energy. For MP UV
these numbers are similar. As the concentration of H2O2 is
Ozone dose (mg L-1)
2.0 3.0 4.0 5.0 6.0
40 60 80 100 120
Ozone dose (M)
 ARTICLE IN PRESS
3702 WAT E R R E S E A R C H 40 (2006) 3695 3704

70

OH Radical Exposure (1013 M min)

60

50
1.43mM H2O2
40

30
0. 29 mM H2O2
20

10 0.06 mM H2O2

0
0 100 200 300 400 500
(a) UV Fluence (mJ L-1)

70
OH Radical Exposure (1013 M min)

60

50
1.52mM H2O2
40

30
0.30mM H2O2
20

10
0.10mM H2O2
0
0 200 400 600 800 1000

(b) UV Fluence (mJ L-1)

Fig. 5 OH radical exposure as a function of UV fluence for (a) LP UV+0.06, 0.29, and 1.43 mM H2O2, and (b) MP UV+0.10, 0.30,
and 1.52 mM H2O2 in Lake Greifensee water. Note the MP UV fluence scale is double the LP UV fluence scale, but the y-axes are
scaled the same. Solid symbols are pH 6.5 data, and open symbols represent pH 8.

Table 3 Local energy cost of hydrogen peroxide in four locations

50% H2O2 30% H2O2 50% H2O2 Germanyd 100% H2O2 Average
California, California, USA Francee
USA USA

H2O2 cost (H$) ($ kg
1 H2O2) 0.60a 0.90a 0.68b n/a 1 Euro
Local electricity cost (E$) ($ 0.065a 0.065a 0.074c n/a 0.085 Euro
kWh
1)
Energy cost of H2O2 (H$/E$) 9.23 13.85 9.19 10.00 11.76 10.81
(kWh kg
1 H2O2)

a
-Patel (2004).b-Tramposch (2004).c-Moody (2003).d-Muller (2001).e-Atofina (2004).

increased, the fraction of total energy of the UV/H2O2 process
due to UV energy is less than 1%.
The addition of hydrogen peroxide to the ozone process
does not improve the overall dOH radical exposure of the
ozone process, as shown in Fig. 4. and with the addition of
hydrogen peroxide energy to the process, one would expect
the process to be more energy intensive than the simple
ozone process for production of dOH radical. This is indeed
the case, as the addition of equimolar concentrations of
hydrogen peroxide to the ozone process increases the energy
requirement by 35%, compared to O3 only. Consequently, the
energy ratios for the UV processes to the equimolar O3/H2O2
in Lake Zurich water process are parallel to the lines in
Fig. 6(b), but shifted down by 35%.
3.4.1. Disregarded costs
This study focused on quantifying the energy costs associated
with different advanced oxidation technologies for the
 ARTICLE IN PRESS
WAT E R R E S E A R C H
3.0
2.5
2.0
log [E(UV)/E(O3)]
1.5
1.0
0.5
0.0
-0.5
-1.0
-14.5 -13.5 -12.5
(a) log(OHCt(M min))
Fig. 6 Energy Ratio of UV to ozone processes as a function of OH radical exposure in (a) Lake Greifensee and (b) Lake Zurich
water at pH 6.5. Solid lines and symbols indicate MP UV data, and dashed indicate LP UV data. The square symbols represent
0.06 mM H2O2 data, triangles are for 0.30 mM data, and circles are for 1.48 mM H2O2 data.
formation of dOH radicals, by using bench scale data to
predict steady state trends. However, many other issues must
be considered when comparing the design of ozone and UV/
H2O2 systems. Neglected cost considerations in this study
included: costs associated with storage, handling, and
pumping of added chemicals (ozone and H2O2), reactor
footprint considerations, destruction or removal of excess
ozone and H2O2 remaining after the treatment process, and
potential formation of undesired byproducts, such as bromate
(von Gunten, 2003b). While the complete costs and benefits of
each technology are of importance in engineering advanced
oxidation technology for a specific water treatment situation,
the data presented in this study provides a fundamental
understanding of dOH radical generation efficiency for ozone
and UV AOPs, to augment some of the practical cost
considerations.
4. Conclusions
Utilizing a method to directly compare the oxidative ability of
ozone and UV/H2O2 processes, the energy required for each
technology to form dOH radicals was determined for distinct
water qualities. Under most of the tested conditions, ozone is
a more energy efficient technology for production of dOH
radical in the waters tested. For UV/H2O2 AOPs, hydrogen
peroxide was the most energy intensive portion of the
processes. The MP UV systems were consistently less efficient
for dOH radical production than were the LP UV systems, due
to the relative inefficiency associated with UV output of MP
lamps and UV light absorption by hydrogen peroxide. Also,
addition of peroxide to the ozone process resulted in a faster
formation of dOH radical, but did not significantly increase
the ultimate dOH radical exposure. The addition of hydrogen
peroxide increased the energy of the process by 35% over the
ozone only process, but reduced contact times to achieve an
d
OH radical exposure.
When a large amount of contaminant oxidation is required,
our results indicate that at low peroxide levels, and high dOH
radical exposure, the UV process can be comparable or less
4 0 (200 6) 369 5 370 4 3703
-11.5 -10.5 -13.0 -12.5 -12.0 -11.5 -11.0 -10.5
(b) log(OHCt(M min))
energy intensive than the ozone processes. However, in most
situations, the ozone process will require less energy to
produce dOH radicals.
Although energy costs are a key component in comparing
UV and ozone systems, it is just one of many considerations.
Ultimate technology analysis must also weigh issues related
to chemical storage, handling, and pumping, reactor footprint
size, destruction or removal of excess chemicals, and
potential for formation of undesirable byproducts.
Acknowledgements
This work was funded in part by EPA Grant #R-829412-01,
Michael Elovitz project manager. Support from Eawag for both
Karl Linden and Erik Rosenfeldt while in Switzerland is
gratefully acknowledged. The authors would like to acknowl-
edge Elisabeth Salhi, Marc Huber, Marc-Olivier Buffle, Michael
Dodd, Laurence Meunier, and Gretchen Onstad at Eawag for
their gracious assistance and patient teaching of some of the
bench scale techniques utilized in this study.
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