ARTICLE IN PRESS

Water Research 39 (2005) 30623072

www.elsevier.com/locate/watres

Destruction of cresols by Fenton oxidation process

V. Kavitha, K. Palanivelu
Centre for Environmental Studies, Anna University, Chennai 600 025, India
Received 13 July 2004; received in revised form 7 May 2005; accepted 10 May 2005
Available online 29 June 2005

Abstract

The present study was used to probe the treatment of simulated wastewater containing cresols by Fenton process.
Experiments were conducted in a batch reactor to examine the effects of operating variables like pH, hydrogen peroxide
concentration (H2O2) and ferrous ion concentration (Fe2+) on chemical oxygen demand (COD) removal. The progress
of the degradation reaction was monitored by the decrease in COD content in the treated solution. The optimal reacting
conditions were experimentally determined and it was found to be [H2O2] 31.64 mM, [Fe2+] 0.90 mM for o- and p-
cresol while 0.72 mM for m-cresol at pH 3.070.2. The degradation efciency for cresol isomers was as high as 82%
within 120 min at optimum conditions. A pseudo-rst-order kinetic model was adopted to represent the Fenton
oxidation for cresols. The mineralization rate for cresols obeys the following sequence: m-4p-4o-. Maximum
degradation occurred at 30 1C for the temperature range of 2050 1C studied. The global activation energy for the rst-
order reaction was estimated to be in the range of 12.9016.25 kJ/mol. Air/nitrogen did not play an active role in
completely mineralizing the organic intermediates at the experimental conditions adopted. Irrespective of the position
of methyl group in o-, m- or p-position, the maximum dissolved organic carbon (DOC) removal efciency was 42%.
Only 2/5th of cresol was mineralized to CO2 by Fenton process. The results showed that the cresols were completely
oxidized and degraded into lower molecular weight aliphatic acids. Among the acids, acetic and oxalic acids were
identied as the major products formed during the degradation.
r 2005 Elsevier Ltd. All rights reserved.

Keywords: Cresols; Fentons reagent; Oxidation; Acetic acid; Oxalic acid; Mineralization

1. Introduction ture to oxidize the persistent organic compounds in a

Environmental pollution and destruction on a global
scale have drawn attention to the vital need for an
environmental clean and friendly chemical process. The
development of process on these areas is the most
important challenge faced by chemical scientists in green
oxidation chemistry. Oxidants like peroxides are acti-
vated by relatively a non-toxic catalyst like iron
(compared to other transition metals) at room tempera-
clean and safe manner leading to the introduction of
Fentons system in wastewater treatment technologies.
Fentons reagent is a mixture of ferrous ion (Fe2+)
and hydrogen peroxide (H2O2) generates hydroxyl
radical (dOH) in situ according to
Fe2 H2 O2 ! Fe3 OH d OH: (1)
d
The generated OH radical can react effectively with a
variety of organic compounds (RH) as follows:

Corresponding author. Tel.: +91 44 22203195; RH d OH ! H2 O R ! further oxidation; (2)

fax: 91 44 22354717.
E-mail address: kpvelu@hotmail.com (K. Palanivelu). R  H2 O2 ! ROH d OH: (3)

0043-1354/$ - see front matter r 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2005.05.011
 ARTICLE IN PRESS
V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072
The high oxidation potential of dOH radical
(E o 2:8 V), can oxidize organic substrates and miner-
alize them to CO2 and H2O. An exhaustive list of
various classes of organic compounds, which can be
treated by Fenton process was reviewed by Gogate and
Pandit (2004) and Neyens and Baeyens (2003). The
coupled Fenton system with ultrasound cavitation was
studied by Lin and Ma (2000) using 2-chlorophenol,
where more than 99% of chlorophenol was decom-
posed. Heterogeneous Fenton systems like Fezeolite
(FeZSM-5) and Felaponite-based nanocomposite
(FeLap-RD), where iron is coated on a solid support
to use it for the degradation studies of phenol
(Fajerwerg et al., 1997) and reactive red HE-3B (Feng
et al., 2003), respectively.
Cresols represent classes of chemical phenolic com-
pounds used extensively in resin manufacturing, herbi-
cide like dinitro-o-cresol (DNOC), pharmaceuticals,
tricresylic acid and surfactants. Wastewater from these
industries together with coal-conversion unit and
petrochemicals (Shivaraman and Pandey, 2000) contain
high concentration of cresol. These compounds possess
a signicant threat to environment, as they are toxic and
refractory in nature. Cresols are classied by USEPA as
persistent, priority, toxic chemical and the quantitative
structureactivity relationship (QSAR) shows chronic
effects at 12 mg/L (Callahan et al., 1979). The LC50 for
cresols towards Salmonid sh, which is the most
sensitive environmental species, is 6.28.4 mg/L.
Treatment methods available for destructing cresols
include biological, chemical and electrochemical oxida-
tions. Microbial degradation of cresols was investigated
by Ahamad and Kunhi (1999) using Psuedomonas sp.
and the rate of degradation of three cresol isomers was
in the order of o-cresolop-cresolom-cresol. Longer
retention time, usually in days to oxidize the organic
compound, is one of the drawbacks in biological
oxidation systems. Electrochemical oxidation of cresols
on Ti/TiO2RuO2IrO2 and carbon cathode was studied
by Rajkumar and Palanivelu (2003) using chloride as a
supporting electrolyte. The formation of halogenated
organic compounds during the electrolytic oxidation
requires carbon polishing as a post-treatment of
electrolytic treated wastewater before discharging.
Thermal decomposition of cresols at 460 1C was
experimented by Martino and Savage (1997) and
Martino et al. (1995) resulting in the formation of
intermediates like hydroxybenzaldehyde, indanone and
CO2. High cost involved in maintaining supercritical
conditions and formation of toxic and higher molecular
weight compounds leads to the emergence of new cost-
effective and clean technologies for treating cresol-
bearing wastewater.
Advanced oxidation processes (AOPs) are commonly
used for remediating wastewaters contaminated with
recalcitrant organic pollutants. The methods are attractive
3063
because of the possibility of mineralizing the target
pollutants. Zheng et al. (1993) reported on ozonation of
cresol isomers with the rate constant for o-, m- and p-
cresol were 32 240, 60 870 and 45 460 M1 s1. Hetero-
geneous photocatalytic oxidation using ultraviolet light/
titanium dioxide (UV/TiO2) was applied to treat cresols
(Wang et al., 1998). Complete removal of cresols
occurred within 2.5 h. Photo oxidation of creosote
components containing xylenols using TiO2 and on
goethite were studied by Terzian and Serpone (1995) and
by Mazellier and Bolte (2000), respectively. Among
different AOPs, homogeneous Fenton process is one of
the powerful oxidative treatments available at room
temperature and pressure with dOH radical as the
reactive species. Recently, the role of dOH radical in
degrading organic compounds has been questioned and
ferrate species [Fe(OH)3(H2O)4]+ has been suggested,
which follows a non-radical mechanism for Fenton
oxidation (Bossmann et al., 1998). Since the products of
both dOH and ferrate degradation pathways cannot be
distinguished (Goldstein et al., 1993), the classical
interpretation of dOH radical as the oxidizing species
in Fenton oxidation has been discussed here.
Most of the previous studies were focused on the
potential viability of Fenton oxidation to destroy cresols
in aqueous solution. The operating parameters like
H2O2 concentration, Fe2+ ion concentration and pH,
which are pertinent for the oxidation reaction, were
studied. However, there have not been extensive studies
that explicitly deal on the effect of gaseous atmosphere
and temperature at the same experimental conditions. In
a way, these parameters could be important in inuen-
cing the Fenton oxidation. In this paper, the effects of
the above parameters together with quantifying the
reaction byproducts formed during the degradation were
examined in order to understand the overall reaction
mechanism involved in Fenton oxidation of cresols.
2. Materials and methods
2.1. Chemicals
Analytical grade reagents, o-, m-, p-cresols were
purchased from CDH, India. All chemicals were used
as received without any further purication and the
stock solutions of cresols were prepared in 0.1 M NaOH.
The initial concentration of cresols used during the
experimental runs was 200 mg/L. Stock solution of H2O2
at 6.76.8 N was prepared by diluting 30% w/v of
peroxide (Qualigens) with distilled water and maintained
at acidic pH. Analytical grade ferrous sulphate hepta
hydrate (FeSO4  7H2O, CDH) was used as a source of
iron and the stock solution was maintained at 90 mM
Fe2+ ion in 0.1 M H2SO4. All stock solutions were
stored in light resistant pyrex glass bottles, refrigerated
 ARTICLE IN PRESS
3064 V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072
at 4 1C. Standards like sodium acetate, sodium oxalate
(BDH) used for ion-chromatograph (IC) system and
potassium hydrogen phthalate (BDH) for dissolved
organic carbon (DOC) analyses were the highest-grade
analytical reagents. Sodium hydroxide (1 N) and sul-
phuric acid (1 N) were used for pH adjustments.
2.2. Experimental procedure
Batch experiments were conducted at room conditions
to determine the effect of pH, H2O2 concentration and
Fe2+ ion concentration during the degradation of
200 mg/L of cresols. In each experimental run, Fe2+
ion and cresol were premixed and diluted to 500 mL
along with distilled water. The reaction was initiated by
adding doses of peroxide into the beaker. During the
reaction, the solution was stirred by magnetic pellet to
ensure its homogeneity. For temperature variation
experiments, the whole set-up was kept at constant
temperature-controlled water bath provided with a
stirrer (KWB-A, Tempo, India) in which temperature
variation occurs within 70.1 1C. All batch tests were
performed in duplicate and in unbuffered solution. The
overall degradation reaction was carried out for 2 h.
2.3. Analyses
The initial pH of the solution was measured using
Elico pH meter LI-120 equipped with a combined
calomelglass electrode. The dissolved oxygen (DO)
content was monitored by means of WTW oximeter
OXI-197 provided with oxygen electrode. Samples
(10 mL) were withdrawn either at predened time
intervals or at the end of 2 h from the batch reactor.
Since Fenton oxidation cannot occur at pH410.0, the
reaction was quenched in the collected samples by
adding 6 N NaOH. The degradation efciency for
cresols was studied by the reduction in chemical oxygen
demand (COD). For COD measurements, the samples
were pretreated with NaOH, heated at 40 1C to remove
any residual H2O2 (Jones, 1999) and determined by
dichromate titrimetric method as described in APHA
et al. (1998). Mineralization of cresols was monitored by
the decrease in DOC content (Lin and Ma, 2000; Feng et
al., 2003; Ma et al., 2000) measured in TOC analyzer
(Analytica Jena Modell, 1997, Germany) equipped with
an autosampler ALS-C-104. Analysis was performed by
acidifying the samples with 15% H3PO4 to remove any
inorganic carbon formed during the oxidation reaction.
The quantitative determination of acetic acid and oxalic
acid (formed as a result of degradation of cresols) were
carried out in IC (Dionex Dx-120) with an Ion Pac AS-
14 (250 mm long) as analytical column. The isocratic
mobile phase consisted of 3.5 mM Na2CO3 and 1.0 mM
NaHCO3, operated at a ow rate of 1.2 mL/min. The
peaks were detected at 2.68 and 7.8570.2 min retention
time for acetic and oxalic acids, respectively. Samples
were treated with 6 N NaOH, ltered through 0.2 mm
Gelman acrodisc before injecting into the column. The
H2O2 concentration in the stock solution and in samples
was determined by standard iodometric titration method
described in Jeffery et al. (1989).
3. Results and discussion
3.1. Fenton process
Preliminary studies on the degradation of cresol
isomers were conducted by varying the initial pH of
the solution from 2.0 to 8.0. Cresols were hardly
decomposed within the experimental time only if H2O2
or Fe2+ ion alone was present in the solution. The
oxidation potential of H2O2 and Fe2+ ion in acidic
solution are 1.77 and 0.77 V, respectively, an oxidizing
power much less than dOH radical to oxidize cresols
effectively. It can be regarded that the degradation of
cresols is possible when both H2O2 and Fe2+ ions are
present in the reacting solution. In an acidic media,
presence of H2O2 and Fe2+ ions generates dOH radical
at room conditions, which has a higher oxidation
potential of 2.80 V to degrade cresols.
When peroxide was added to an acidic solution
containing cresol and Fe2+ ion, the colour of the
solution changed from limpid to brown and turbid
within 10 min of the reaction time and nally to
light yellow and limpid, signifying the completion of
the reaction. As it is evident from the Eq. (1), the
concentration of H2O2, Fe2+ ion and pH, which are
crucial in generating the dOH radical, ultimately
determines the degradation efciency for cresols. Hence,
experiments were conducted in batch reactor to study
the effect of these operating variables on the degradation
of cresols. The degradation efciency was monitored by
measuring residual COD at the end of the reaction time.
3.2. Optimization of reaction conditions during Fenton
oxidation of cresols
3.2.1. Effect of initial pH on degradation of cresols
The effect of pH on the degradation of cresols is
illustrated in Fig. 1 and the experiments were performed
at room conditions in the pH range of 2.06.0 by
maintaining the H2O2 concentration and Fe2+ ion
concentration at 25.8 and 0.8 mM, respectively. The
initial pH value affects the degradation of cresols
signicantly by directly inuencing the generation of
d
OH radical. Maximum degradation efciency of 82%
was observed for all the cresol isomers in a narrow pH
range of 3.03.5. The optimum range obtained for
cresols is in accordance with the degradation for several
organic compounds like phenol (Eisenhauer, 1964)
 ARTICLE IN PRESS
V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072 3065

90 5 experiments were conducted at an initial pH of

4.5 3.070.2, without adding any buffers for pH adjustments
80
during the progress of the reaction.
4
Degradation efficiency (%)

70
3.5
60 3.2.2. Effect of initial H2O2 concentration on degradation
3 of cresols

50
40
30
DE-o-cresol DE-p-cresol
20 DE-m-cresol pH-o-cresol
pH-p-cresol pH-m-cresol
10
0 0
2 2.5 3 3.5 4 4.5 5 6
Initial pH
Fig. 1. Effect of initial pH on degradation efciency for cresols.
DE and pH represents the degradation efciency and nal pH
curves for the cresols studied (conditions: [Cresols] 1.85 mM,
[H2O2] 25.8 mM, [Fe2+] 0.8 mM).
p-nitrophenol (Ma et al., 2000) and p-hydroxybenzoica-
cid (Rivas et al., 2001). It may, therefore, be suggested
that the optimum pH obtained is the most ideal pH
(3.070.2) for the generation of dOH radical rather than
specic to a particular organic substrate. The drop in
degradation efciency at pH44.0, is due to precipita-
tion of Fe(OH)3, which lowers the concentration of free
soluble iron species available for reacting with peroxide.
Hence, lesser concentration of dOH radical is generated
for oxidizing cresols and consequently the degradation
efciency decreases. Besides, the oxidation potential of
d
OH radical decreases with increasing pH. Bossmann et
al. (1998) reported the oxidation potential for the redox
couple dOHaq/H2O is 2.59 V at pH 0 and decreased to
1.64 V at pH 14.0. On the other hand, at very low pH
values (o 2.0) the reaction is slowed down due to
the formation of complex species [Fe(H2O)6]2+, which
Final pH
2.5 Hydrogen peroxide plays the role of an oxidizing
agent in Fenton process. The effect of change in H2O2
2
concentration on degradation efciency for cresol
1.5 isomers is depicted in Fig. 2. The concentration of
H2O2 was varied from 0 to 50 mM at room conditions
1
while keeping the Fe2+ ion concentration at 0.8 mM and
0.5
pH at 3.070.2. The degradation efciency increases
with increasing H2O2 concentration, due to incremental
d
OH radical produced by the reaction as shown in
Eq. (1). Maximum degradation efciency was attained
at 31.64 mM for all the cresol isomers studied. Further
addition of H2O2, did not improve the degradation
efciency, may be due to self-decomposition of H2O2 as
in Eq. (4). Moreover, the excess H2O2 react with ferric
ion (Fe3+) to form weaker hydroperoxyl radical (HO2  )
as presented in Eqs. (5) and (6), which is not as active as
d
OH radical towards cresols degradation
2H2 O2 ! 2H2 O O2 ; (4)
Fe3 H2 O2 ! Fe2 HO2  H ; (5)
d
OH H2 O2 ! HO2  H2 O: (6)
From the results it can be drawn that maximum
degradation occurred with H2O2 to cresol molar ratio of
approximately 17. The stoichiometric amount of H2O2
required for total mineralization of cresol isomers was
90
80
Degradation efficiency (%)

reacts more slowly with peroxide compared to that of

[Fe(OH)(H2O)5]2+. In addition, the peroxide gets
70
solvated in the presence of high concentration of H+
ion to form stable oxonium ion [H3O2]+. An oxonium
ion makes peroxide electrophilic to enhance its stability 60 DE-o-cresol
and presumably reduces substantially the reactivity with DE-m-cresol
Fe2+ ion (Kwon et al., 1999). Therefore, the concentra- 50
DE-p-cresol
tion of dOH radical from Eq. (1) would decrease at pH
2.0 resulting in decrease in the degradation efciency.
40
Hence, low degradation efciency was observed at high
and very low pH values.
During degradation experiments for pH variation 30
0 10 20 30 40 50
from 3.0 to 4.5, it was noticed that the pH of the treated
H2O2 concentration (mM)
solution dropped to 2.570.2 indicating the presence
of degraded products which are acidic in nature. A drop Fig. 2. Effect of initial H2O2 concentration on degradation
in pH was reported by Lu et al. (1999) during the efciency for cresols (conditions: [Cresols] 1.85 mM,
degradation study on dichlorvos. However, further pH 3.070.2, [Fe2+] 0.8 mM).

3066 V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072
obtained from
C7 H8 O 17H2 O2 ! 7CO2 21H2 O:
The molar ratio (H2O2/cresol) observed during the
present study was exactly same as the stoichiometric
ratio (1:17). However, complete degradation (100%)
was not observed at the stoichiometric ratio, which may
be attributed to the presence of recalcitrant organic
molecules-like acetic acid and formic acid (Bigda, 1995)
formed during Fenton degradation process.
3.2.3. Effect of initial Fe2+ ion concentration on
degradation of cresols
To elucidate the role of Fe2+ ion on degradation of
cresols, a series of experiments were performed at room
conditions by varying the concentration of Fe2+ ion
from 0 to 1.0 mM for xed H2O2 concentration of
31.64 mM and at pH 3.070.2. The degradation ef-
ciency for cresol isomers with various Fe2+ ion is
illustrated in Fig. 3. At low Fe2+ ion concentration
(40.4 mM), the degradation efciency was less than
50%. The efciency increased progressively with in-
crease in Fe2+ ion concentration due to higher amount
of dOH radical generated through Eq. (1). Maximum
degradation efciency of about 82% was achieved at
0.90 mM of Fe2+ for o- and p-cresol while 0.72 mM for
m-cresol. Further increase in Fe2+ ion concentration did
not correspondingly increase its reactivity probably due
to direct reaction of dOH radical with metal ions
(Joseph et al., 2000) as follows:
Fe2 d OH ! Fe3 OH :
90
80
Degradation efficiency (%)
70
60
50
40
30
0 0.2 0.4 0.6
Fe2+ ion concentration (mM)
Fig. 3. Effect of initial Fe2+ ions concentration on degradation
efciency for cresols (conditions: [Cresols] 1.85 mM,
pH 3.070.2, [H2O2] 31.64 mM).
ARTICLE IN PRESS
Of the three isomers, the maximum efciency was
attained at low concentration of Fe2+ ion (0.72 mM) for
(7)
m-cresol, may be due to higher susceptibility of m-cresol
towards Fenton oxidation compared to other cresol
isomers. Molar ratio of H2O2/Fe2+ of 35 was observed
for o- and p-cresol while molar ratio of 44 for m-cresol at
their maximum degradation efciency. Tang and Huang
(1997) and Ruppert et al. (1994) recommended an
optimal molar ratio (H2O2/Fe2+) of 10:1 to 40:1 for
Fenton oxidation of chlorinated aliphatics and
4-chlorophenol, respectively, which supports our ob-
servation on cresols. The results show that the optimal
molar ratio of chemicals (H2O2:cresol:Fe2+) for Fenton
oxidation of cresol at pH 3.070.2 is 17:1:2.1 for o-and
p-cresol and 17:1:2.6 for m-cresol.
3.3. Global kinetics for Fenton oxidation of cresols
In Fenton oxidation, (as presented in above discus-
sion) dOH radical play a vital role in oxidizing the target
organic contaminants, in our case, cresols at rates close
to diffusion rate in water (1010 M1 s1). The reaction
rate depends directly on the concentration of cresol and
the dOH radical generated (Zoh and Stenstrom, 2002),
leading to second-order rate equation as follows:
dC cr =dt kcr C cr C d OH , (9)
where C cr is the concentration of cresols, COH is the
hydroxyl radical concentration and kcr is the second-
order rate constant. In the presence of excess of reagents
namely H2O2 concentration, Fe2+ ion concentration
(8) which ultimately results in generation of high concen-
tration of dOH radical compared to the concentration of
organic substrate, the above Eq. (9) can be reduced to a
pseudo-rst-order rate equation as given by
dC cr =dt k0cr C cr , (10)
where k0cr
is the pseudo-rst-order rate constant. When
t 0, C cr is equal to C cr;t0 and the solution of the
Eq. (10) becomes
ln C cr =C cr;t0 k0cr t. (11)
DE-o-cresol
DE-m-cresol The kinetics of total mineralization of cresols has been
DE-p-cresol followed by measuring the residual DOC. Pseudo-rst-
order rate constant for cresol isomers can be obtained
through a linear least-square t of mineralization data to
Eq. (11) and is presented in Fig. 4. The rate constant for
o-, m- and p-cresol are 0.0075, 0.0086 and 0.0081 min1,
respectively. The mineralization data reveals that among
the cresol isomers, increasing rate of mineralization
follows the sequence of o-op-om-cresol, which is in
0.8 1
accordance with the results observed by Zheng et al.
(1993) during the degradation of cresols by ozone. Half-
life (t1=2 ) values for cresols can be calculated by applying
the corresponding rate constant values to Eq. (12) and
found to be 92.40, 80.88 and 85.55 min for o-, m- and
 ARTICLE IN PRESS
V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072
Fig. 4. Mineralization kinetic rate for cresols during Fenton
oxidation. Inset are the concentration curves for cresols
(conditions: [Cresols] 1.85 mM, pH 3.070.2, [H2O2]/
[Fe2+] 35 for o-, p-cresol and 44 for m-cresol).
p-cresol, respectively
t1=2 0:693=k0cr . (12)
The observed results of the present study can be
explained from orthopara directing effect of phenolic
OH group. As it is known, both the hydroxyl group
(OH) in the phenolic ring and the methyl group
(CH3) are orthopara directing with activation.
Hydroxyl radical, being an electrophilic reagent attacks
the electron-rich carbon atom of cresol resulting in
oxidation of substrates. Among the cresol isomers, when
the CH3 group is in m-position to OH group, two
ortho and one para position are susceptible for dOH
radical attack while in o- and p-cresol, only one ortho,
one para and two ortho positions are left for dOH attack
which results in faster mineralization rate for m-cresol
compared to o- and p-cresol. With respect to o- and
p-cresol, the reaction rate for o-cresol is less than for
p-cresol and it could be attributed to stereochemical
inhibition to dOH attack, due to close proximity of
OH and bulky CH3 groups on the aromatic ring
resulting in slight retardation in rate.
3.4. Temperature dependence on degradation of cresols
A series of batch experiments were conducted to
determine the effect of reaction temperature on the
overall degradation of cresols. The initial H2O2 con-
centration and Fe2+ ion concentration were 31.64 and
0.90 mM for o- and p-cresol while 0.72 mM for m-cresol.
The initial pH was xed at 3.070.2 and the reactions
were performed by varying the temperature from 20 to
50 1C. Fig. 5 shows the result of o-, m- and p-cresol
degradation at different temperatures. Maximum de-
gradation efciency was observed at 30 1C, suggesting
3067
the optimal temperature for the oxidation reaction.
Above 30 1C the degradation efciency was levelled off,
presumably due to the presence of intermediates, which
are not amenable to Fenton oxidation. Below the
optimum temperature (30 1C), there was a sharp decline
in the efciency because of slow reaction rates between
d
OH radical and organic cresol isomers. The result
obtained is in agreement with results reported by Rivas
et al. (2001) and Lin and Lo (1997).
The degradation of cresol isomers was very fast
during the initial stages of the reaction (i.e. up to 15 min)
and after 60 min, only 5% degradation occurred.
Increase in temperature increased the rate of degrada-
tion for cresols. The observed degradation data (based
on residual COD) were tted into pseudo-rst-order
kinetic model as follows:
ln C t =C 0 k0 t, (13)
where C 0 and C t are the COD values at time t 0 min
and at time t min and k0 is the pseudo-rst-order rate
constant. The rate constants for different cresols are
given in Table 1. The results show excellent agreement
between pseudo-rst-order reaction mechanism and the
temperature studied, with r2 ranging between 0.9935 and
0.9991. The observed rate constants at different tem-
peratures can be valid in the pH range of 3.03.5, H2O2
concentration of 3135 mM and Fe2+ ion concentration
of 0.720.90 mM for 1.85 mM of cresol.
The temperature dependence on the observed pseudo-
rst-order rate constant can be represented by Arrhenius
equation as follows:
k A expE a =RT , (14)
where A is the frequency factor, E a is the activation
energy, R is the gas constant and T is the temperature.
Fig. 6 shows the Arrhenius plot of the reaction rate
constant for cresol isomers and slope Ea/R. The
corresponding activation energy for o-, m- and p-cresol
is 16.25, 12.90 and 14.95 kJ/mol, respectively. Low
activation energy was observed for m-cresol compared
to o- and p-cresol, can be attributed to +I effect of
CH3 group in meta position which increases the
electron density of phenoxide ring for dOH attack. In
general, low activation energies observed for cresol
isomers are well matched to the ndings of Lin et al.
(1999), reported activation energies of 10.62 and 8.08 kJ/
mol for alkyl benzene sulphonate (ABS) and linear
alkylbenzene sulphonate (LAS), respectively. Lin and
Lo (1997) also experienced low activation energy for
COD depletion in treating desizing wastewater. Only
a small difference in activation energy was noted
among cresol isomers indicating that Fenton oxidation
proceeds through a common degradation mechanism
irrespective of o-, m- and p-substituents in the aromatic
phenolic ring.
 ARTICLE IN PRESS
3068 V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072

2.1 1.8
o - cresol m - cresol 2
1.6 p - cresol
1.8 1.8
1.4 1.6
1.5
1.2 1.4
-ln (Ct/C0)

-ln (Ct/C0)

-ln (Ct/C0)
1.2 1 1.2
1
0.9 0.8
0.8
0.6
0.6 0.6
0.4
0.4
0.3
0.2 0.2
0 0 0
0 20 40 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min) Time (min)

Fig. 5. Temperature dependence on Fenton oxidation for cresols [conditions as in Fig. 4 ((~), (), (m), and (K) 20, 30, 40 and
50 1C, respectively)].

Table 1
Pseudo-rst-order rate constant (min1) for cresols at different temperatures

T (1C) o-cresol m-cresol p-cresol

k (min1) r2 k (min1) r2 k (min1) r2

20 0.0152 0.9987 0.0211 0.9987 0.0172 0.9947

30 0.0206 0.9935 0.0258 0.9969 0.0236 0.9987
40 0.0259 0.9954 0.0315 0.9991 0.0297 0.9977
50 0.0287 0.9991 0.0346 0.9975 0.0327 0.9964

-3.1 100 14
DE-Air DE-Nitrogen
ym-cresol = -1.5528x + 1.452
DE-Normal DO-Air
12

Dissolved oxygen (DO, mg/L)

-3.3 DO-Nitrogen DO-Normal
80
Degradation efficiency (%)

yp-cresol = -1.7984x + 2.1415

10
yo-cresol = -1.954x + 2.5184
-3.5 60
o-cresol 8
m-cresol
p-cresol
ln k

-3.7 6
40

4
-3.9
20
2
-4.1
0 0
0 1 5 10 15 30 45 60 90 120
-4.3 Time (min)
3 3.1 3.2 3.3 3.4 3.5
(1/T)*103 (K-1) Fig. 7. Effect of gaseous atmosphere on degradation efciency
for o-cresol (conditions: [o-cresol] 1.85 mM, pH 3.070.2,
Fig. 6. Arrhenius plot of Fenton oxidation rate constants for [H2O2]/[Fe2+] 35).
cresols.

3.5. Effect of gaseous atmosphere on degradation of o-
cresol
Kinetic plot on the decrease in COD in the solution as
a function of time for normal, air and nitrogen-saturated
solution for o-cresol is shown in Fig. 7. At normal,
air and in nitrogen-saturated solutions, the degradation
efciency for o-cresol remained same. In nitrogen-
saturated solution, the initial degradation efciency was
less compared to normal and air-saturated conditions.
 ARTICLE IN PRESS
V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072
During air/nitrogen-saturated solution, a decrease in
DO in the range of 4.320.4 mg/L was observed in the
initial stages of the reaction up to 60 s and then the DO
increase. Transient increase in DO was observed from 5
to 45 min, and then it decreased to its initial DO value.
In normal conditions, the initial DO was 7.4 mg/L. As
peroxide was added, the DO decreased to 6.75 mg/L at
60 s and to 0.99 mg/L within 10 min of the reaction time.
More than 70% of cresol was degraded during this time
interval (within 5 min) suggesting a rapid consumption
of H2O2 in the form of dOH radical for the degradation
process. The DO value increased after 5 min continu-
ously and reached up to 13 mg/L at 45 min which then
decreased to its initial value of 8 mg/L. Increase in the
DO was due to slow consumption of dOH radical by
recalcitrant organic intermediates formed as a result of
degradation for o-cresol and rapid production of O2 by
the breakdown of peroxyl radical catalyzed by Fe3+ ion
together with self-decomposition of H2O2 as shown
below in Eqs. (15) and (16). Between 5 and 120 min of
the reaction time interval, only 12% degradation for
o-cresol was noted. The DO proles observed during the
present study was similar to that reported by Lu et al.
(1999) for dichlorvos, where DO dropped immediately
at the start of the Fenton reaction and then increased
Fe3
2HO2  ! H2 O2 O2 , (15)
2H2 O2 ! 2H2 O O2 . (16)
In air-saturated solution, the degradation efciency
remained same as in normal Fentons system, may be
the reaction of air with intermediate organoradicals (as
in Eq. (17)) was insensitive at the experimental condi-
tions adopted
H2 O
R  O2 ! RO2  ! ROH HO2  (17)
Moreover as seen from the DO value, oxygen
saturation was attained during the degradation in both
normal/air-saturated solutions, thereby resulting in
similar degradation efciencies. Perez et al. (2002)
experienced that bubbling of oxygen through paper
and pulp efuent in Fenton treatment, did not improve
the reaction efciency. In nitrogen-saturated solution,
the degradation efciency remained almost same as in
normal/air-saturated solution, with a slight decrease in
its initial efciency. As seen from Fig. 7, in nitrogen-
saturated solution also the DO level increased to
6.88 mg/L at 45 min as against the background level of
2.0 mg/L mainly due to reactions presented in Eqs. (15)
and (16). These reactions suggest that the organoradicals
proceed further without any retardation at the experi-
mental peroxide concentrations adopted. Hence, it may
be regarded that the inuence of gaseous atmosphere in
degrading cresols by Fenton oxidation is insensitive at
high peroxide concentration.
3069
3.6. Mineralization/intermediate products
The mineralization efciency for cresol isomers at
optimum conditions is depicted in Fig. 8. The efciency
was negligible during the initial stages of the reaction
(i.e. up to 5 min) suggesting slow conversion of parent
cresol compounds to CO2. Between 10 and 60 min,
increase in the mineralization efciency indicates the
possible rupture of aromatic ring to aliphatic products.
The nal slowing down in efciency is due to the
resistant nature of intermediate compounds originated
from the cleavage of aromatic ring. The mineralization
efciency for cresol isomers was 42%, irrespective of the
position of methyl group on the phenolic ring. The result
suggests that after initial hydroxylation reaction, sub-
sequent oxidation reaction proceeds by common degra-
dation mechanism. Indeed, only a little loss in DOC was
noted for cresol isomers, suggesting the presence of
intermediate organic species. Ma et al. (2000) have
experienced only 30.6% removal of DOC during the
degradation of p-nitrophenol by Fenton process. Safar-
zadeh-Amiri et al. (1997) also reported that mineraliza-
tion of organic compounds by Fenton process will not
exceed 50% and depends on the reagent concentration.
The average oxidation state of the treated solution
was assessed by a ratio of COD/DOC, using Eq. (18)
given by Bowers et al. (1989)
Average oxidation state 4DOC  COD=DOC;
(18)
where DOC and COD are, respectively, expressed in
moles of C/L and moles of O2/L. The oxidation state for
cresol isomers before oxidation was 0.856 and after
oxidation for o-, m- and p-cresol were 2.337, 2.592 and
2.315, respectively. The data show conclusively that
ultimate conversion of organic carbon to CO2 did not
45
40
Mineralization efficiency (%)
35
30
o-cresol
25
m-cresol
20 p-cresol
15
10
5
0
0 20 40 60 80 100 120
Time (min)
Fig. 8. Mineralization efciency for cresols during Fenton
oxidation (conditions as in Fig. 4).

3070 V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072
take place but rather the parent cresol compounds were
drastically altered as shown by change in sign of the
oxidation state from high negative to positive values.
The average oxidation state for the treated solution has
a value close to 2.5 (is a value representative of highly
oxidized substance) indicating that the byproducts
formed during the degradation of cresol were highly
oxidized and less toxic in nature.
The peroxide was consumed as the reaction proceeded
for the generation of dOH radical, which ultimately
resulted in the degradation of cresols. It was found that
the concentration of peroxide decreased from the initial
value of 1075 mg/L to around 725700 mg/L within
5 min, where only 910% mineralization occurred
resulting in the peroxide consumption of 3034%. At
the end of the reaction, only 5055 mg/L of peroxide was
left in the reacting solution. Considering the detection
limit for peroxide measurement is about 90 mg/L, it may
be regarded that almost all the peroxide was utilized
during the degradation studies.
Analysis of possible intermediate products indicates
the presence of oxalic acid and acetic acid during the
degradation of all cresol isomers and is illustrated in
Fig. 9. The concentration of oxalic acid and acetic acid
increased as the reaction proceeded and reached a steady
value after 60 min of the reaction time. Kang et al.
(1999) and Hess et al. (2003) reported the presence of
oxalic acid during the degradation of dinitrophenol and
nitro aromatic compounds by Fenton process. A
substantial amount of acetic acid was formed during
the initial stages of the reaction indicating the possible
The optimum operating conditions for Fenton
cleavage of alkyl group in the phenolic ring. Both oxalic
acid and acetic acid were formed almost in same amount
(on weight basis) and their values ranged from 110 to
142 mg/L. As it is evident from Fig. 9, both these acids
1.8
Fenton process was modeled into pseudo-rst-order
Ox-o-cresol Ox-m-cresol
1.6 Ox-p-cresol Ac-o-cresol
Ac-m-cresol Ac-p-cresol
1.4
Oxalic acid(Ox, mM)
1.2
1
Increase in temperature did not affect the degrada-
0.8
0.6
0.4
0.2
Degradation efciency was unaltered in the presence
0 0
0 1 5 10 15 30
Time (min)
Fig. 9. Concentration proles of acetic acid and oxalic acid
42% mineralization of cresols was observed at
formed during Fenton oxidation of cresols (conditions as in
Fig. 4).
ARTICLE IN PRESS
were accumulated during the progress of the reaction
and the oxidation did not proceed further to complete
conversion to CO2. Sedalk and Andren (1991) reported
a contrasting role of these acids in Fenton oxidation by
forming potentially stable complexes like ferric oxalate
and ferric acetate. In this way, the intermediates formed
(oxalic acid and acetic acid) preclude further oxidation
reactions by deactivating Fe2+ ion in dOH radical
production. Bigda (1995) also reported on the refractory
nature of these acids towards Fenton oxidation.
The measured DOC when compared to the calculated
DOC (carbon equivalent of the detected intermediates)
indicated more than 92% residual carbon in cresol
oxidation was accounted for oxalic acid and acetic acid.
The results imply that majority of the aromatic organic
carbon in cresol was converted into aliphatic com-
pounds namely oxalic acid and acetic acid suggesting
they were the nal products formed during Fenton
oxidation for cresol isomers irrespective of the position
of methyl substituent on aromatic phenolic ring.
4. Conclusions
Treatment of simulated wastewater containing cresols
by Fenton process has been taken into consideration in
the present study. On the basis of the results obtained,
the following conclusions have been made:
oxidation of cresol isomers were 31.64 mM [H2O2],
0.90 mM [Fe2+] for o- and p-cresol while 0.72 mM
for m-cresol at an initial pH of 3.070.2. Under these
conditions, maximum degradation of 82% was
observed for all the cresol isomers.
2.5
kinetics, since peroxide and Fe2+ ion are in excess
concentration to the substrate. The rate of miner-
2 alization obeys the following sequence: m-4p-4o-
cresol with t1=2 values ranging from 80.88 to
Acetic acid (Ac, mM)
92.40 min.
1.5
tion efciency for cresols. The activation energy for
cresol isomers by Fenton process was estimated to be
1
in the range of 12.9016.25 kJ/mol. Low activation
energy suggests high effectiveness of cresol isomers
0.5
towards Fenton reaction.
of air/nitrogen atmospheres at the experimental
conditions suggesting that both these gases can
45 60 90 120 participate in Fenton oxidation reaction only at low
peroxide concentration.
optimum conditions for all the cresol isomers.
Short-chain aliphatic compounds like oxalic acid
 ARTICLE IN PRESS
V. Kavitha, K. Palanivelu / Water Research 39 (2005) 30623072
and acetic acid were quantitatively identied. These
ring cleaved products were the main components
contributing for the residual organic matter in the
treated solution. Further removal of these com-
pounds, requires alternative treatment methods like
applying UV light to Fenton system (photo-Fenton)
or precipitate the acids formed with lime as calcium
carboxylates.
Fenton process could be an effective pre-treatment
method to destroy cresols into products, which are
more amenable to biological treatment.
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