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Treatment of Chlorophenols from Wastewaters by

Advanced Oxidation Processes

Swati Sharma , Mausumi Mukhopadhyay & Z. V. P. Murthy

To cite this article: Swati Sharma , Mausumi Mukhopadhyay & Z. V. P. Murthy (2013) Treatment
of Chlorophenols from Wastewaters by Advanced Oxidation Processes, Separation & Purification
Reviews, 42:4, 263-295, DOI: 10.1080/15422119.2012.669804

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Separation & Purification Reviews, 42:263–295, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 1542-2119 print/1542-2127 online
DOI: 10.1080/15422119.2012.669804

Treatment of Chlorophenols from Wastewaters

by Advanced Oxidation Processes

SWATI SHARMA1,2 , MAUSUMI MUKHOPADHYAY1 ,

and Z. V. P. MURTHY1
1
Department of Chemical Engineering, Sardar Vallabhbhai National Institute
of Technology, Surat, Gujarat, India
2
Department of Chemical Engineering, Sarvajanik College of Engineering
and Technology, Surat, Gujarat, India

The ubiquitous presence of chlorophenols (CPs) in the natural

environment illustrates the seriousness of CP pollution and the
importance of an effective method for treating wastewaters con-
taining CPs. The limitations of conventional wastewater treatment
methods to effectively degrade/remove CPs having recalcitrant
properties mandates the search for newer cost effective treatment
technologies to be developed to meet the stringent environmental
regulations. Advanced oxidation processes (AOPs) have evolved
as the most promising techniques as they facilitate a substantial
amount of chemical oxygen demand (COD) and total organic
carbon (TOC) removal from industrial effluents. An extensive lit-
erature review of the widely used methods for CPs degradation is
presented with due focus on AOPs. The overall objective is to review
CP degradation by AOPs at length, with regard to specific reaction
conditions, UV irradiation intensity, oxidants, degradation kinetics
and intermediates/products formed thereof.

KEYWORDS Degradation, advanced oxidation processes,

wastewater, photolytic

Received 8 December 2011, Accepted 22 February 2012

Address correspondence to Z. V. P. Murthy or Mausumi Mukhopadhyay,
Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology,
Surat 395007, Gujarat, India. E-mail: [email protected], [email protected], or
[email protected]

263
264 S. Sharma et al.

INTRODUCTION

Chlorophenols (CPs) represent a group of contaminants frequently found in

various industrial effluents and hazardous waste sites. Included in the list of
priority organic pollutants, CPs are present in wastewaters as by-products
of pulp and paper, dyestuff, pharmaceutical and agrochemical industries
(1). CPs may be present in the aquatic environment in free or complex
form, adsorbed on suspended inert solid or benthic sediments, or carried
in biological tissues. They are also detected in surface and groundwaters
(2). CPs are versatile intermediates in chemical synthesis because both the
hydroxyl group and the aromatic ring can react by electrophilic and nucle-
ophilic substitution (1). CPs are used as antiseptics, wood preservatives,
herbicides, insecticides and fungicides (3). Formed as byproducts during
chlorination of drinking water and incomplete incineration, CPs are highly
toxic, poorly biodegradable and exhibit carcinogenic and recalcitrant proper-
ties (4). CPs are known to be endocrine disruptors. Toxic reference values of
43.8, 36.5 and 13.0 g/L are, respectively, suggested for 2-monochlorophenol
(2-MCP), 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) in sur-
face waters, and maximum average values should not exceed 2, 4.4 and
0.055 mg/L (2).
Toxicity and persistence of CPs have aroused a great deal of public
concern to restore contaminated sites to avoid further risks to the environ-
ment (5). Complex toxicological effects and omnipresence make remediation
research an important task in environmental chemistry (6). In India, the
Central Pollution Control Board (CPCB) has set the limit of 5.0 mg/L for all
phenols. CPs are banned from use, production, import and export in India.
The stockpiles of obsolete CPs exist, posing a major threat to the environ-
ment. There is a dearth of information on these stockpiles in any country;
hence extensive investigation is required to establish the total quantity of
stockpiles.
Abundant literature supporting CP degradation by ultraviolet (UV), inor-
ganic oxidants, their kinetic aspects (7–10) and organic oxidants (11–14), is
available. The objective of this review is to compare and discuss advanced
oxidation processes (AOPs) for CP removal. This review further focuses
on the gradual transition of treatment methods from simple conventional
methods to the various aspects of AOPs as powerful techniques in CP
degradation/mineralization.

TRANSITION OF TREATMENT TECHNIQUES IN CP DEGRADATION

Conventional CPs treatment techniques include physical/chemical methods

or a combination of both. They are mainly employed as pretreatment pro-
cesses to prepare the wastewater for further treatment. CPs degradation using
 Chlorophenol Remediation in Wastewater 265

carbon adsorption (15, 16), alkaline permanganate (7), bimetallic systems

(17) and biological methods (18–21) are widely reported.
Anaerobic and aerobic biodegradation have been shown to be effective
in removal of chlorinated phenols (18–22). Anaerobic degradation of CPs
is known to occur under low reduction potential (methanogenic or sulfido-
genic conditions), which may limit its application in the field. Biodegradation
of 4-CP is found to be slow and incomplete yielding more toxic by-products
(5, 23). Aerobic degradation involves ring cleavage prior to dechlorination
and such ring-cleaved products may be toxic if accumulated in the environ-
ment (18). The intermediate products of degradation are at times reported
to be more toxic/refractory than the parent compound (24). During biologi-
cal treatment, microorganisms are easily inhibited by toxic CPs. Additionally
the biomass is easily lost from the system thereby reducing the treatment
efficiency drastically. Biological methods are amenable, only in a limited
number of ways, for biodegradable pollutants in industrial effluent.
Chemical treatment methods can prove costly to the user when the
active agent cannot be recovered for reuse in successive treatment cycles.
Thermal treatments present considerable emission of other hazardous com-
pounds. Volatilization transfers the CPs from the water to the air but does
not otherwise affect it. Electrochemical reductive dechlorination of PCP
is also reported to result in the accumulation of partially/dechlorinated
intermediates. Conventional wastewater treatment methods tend to transfer
waste components from one phase to another instead of effecting a com-
plete removal. All these processes thus have their inherent limitations such
as low rates of degradation/ mineralization.
In the recent years, AOPs involving hydrogen peroxide, ozone and/or
Fenton reagents, with/without a source of UV light are reported to be useful
for the oxidation of organic pollutants in wastewaters (25). It has also been
reported that the use of UV coupled with inorganic oxidant gives promising
results compared to UV or oxidant alone (25). In wake of these facts, AOPs
offer a better choice in overcoming the limitations posed by the conventional
methods. Consecutively, the following section is devoted to a detailed dis-
cussion of AOPs, including nonphotolytic/photolytic processes, employed
for CP degradation with due regard to process conditions, UV irradiation
and degradation products formed.

ADVANCED OXIDATION PROCESSES

AOPs are defined (26) as water treatment processes near ambient tempera-
ture and pressure. AOPs tend to offer a highly reactive, nonspecific oxidant
namely hydroxyl radical (OH∗ ) (27, 28), which is the principal agent respon-
sible for the oxidation of numerous aqueous organic contaminants (29, 30).
The OH∗ is short lived, unstable and must be continuously produced in situ
266 S. Sharma et al.

by means of chemical or photochemical reactions (26, 31, 32). AOPs are

classified as heterogeneous and homogeneous by considering the phases in
which the processes take place. The literatures available with regard to CP
degradation addressing the specific process conditions, concentration range
and so forth are discussed at length and presented in brief in Table 1 (8, 9,
14, 33–38).
It is reported (9) that the addition of small quantities of Fe3+ or Fe2+
significantly accelerates the degradation rate. Under the optimal conditions,
electro-Fenton method was used to treat various CPs including PCP, 4-CP, 2,4-
DCP, 2,4,6-TCP and their aqueous mixture solutions. Using electro-Fenton
method, the degradation sequence with various CPs is obtained as 2,4-
DCP > 2,4,6-TCP > PCP > 4-CP. This is attributed to the competition of
hydroxyl attack dechlorination and electrochemical reductive dechlorination
(9). It is reported (33) that N-doped TiO2 showed higher degradation effi-
ciency under UV and visible light irradiations. The degradation rate of 4-CP
under sunlight irradiation for 6 h is 82.0%, which is noted to be higher
than 66.2% of the pure TiO2 , 60.1% or 65.2% of the N-doped TiO2 using
single ammonia or hydrazine hydrate as precursor. The catalysts derived
from ammonia, hydrazine hydrate and their mixtures are denoted as TN1,
TN2 and TN3, respectively. Apparent reaction rate constants of TN1, TN2 and
TN3 are 0.00199, 0.00185 and 0.00232 min−1 , respectively. Among the
nitrogen-doped TiO2 , TN3 is of lower activity than both of those of TN1 and
TN2 under UV irradiation (33).
When doped TiO2 is used, degradation rate, increases with increase in
concentration of 4-CP up to 250 mg/L and then decreases (34). It enhances
with doped nano-TiO2, being favorable in the neutral pH range, faster at
lower pH values for o-CP and p-CP. It is noted to increase with increase
in catalyst weight up to an optimum loading. Pseudo–first-order kinetics
is exhibited at low 4-CP concentration (34). The authors (34) report that
with the use of bulk TiO2 like charge carrier, recombination occurs within
nanoseconds and prevents utilization of visible light. Entry of Mg2+ into the
lattice of nano-TiO2 creates charge due to blocking of active sites in the
nanosized TiO2 particles. The authors (34, 35) propound that ZnO is stable
and undergoes photocorrosion to a negligible extent. Photocatalytic activity
of ZnO is retained up to five cycles, and it is reported to be a suitable
alternative to TiO2 and proved to be more efficient than TiO2 . It is also
reported that increased concentration of dissolved O3 does not result in
better CP removal (34, 35).
Removal of 4-CP is reported (8) to the extent of 99.8% and 2,4-DCP,
98.9%. High degree of mineralization is also noted. The authors report that
the efficiency is higher as the emission of O3 takes place in a closed system
(8). Concentrations of residual ozone after ozonization are found very low.
Degradation rate is in decreasing rate of magnitude 2,3,4,6-tetrachlorophenol
(2,3,4,6-TeCP) > 2,4,6-TCP > 2,4-DCP > 2-CP > 4-CP in acidic media
 TABLE 1 Summary of treatment techniques reported for CP degradation

Treatment technique Target compound Specific process conditions Concentration range Ref.

Electro-Fenton 4-CP, PCP, 2,4-DCP, pH > 7 CP, 16 mg/L (9)

2,4,6-TCP Na2 SO4, 19860mg/L.
UV/organic oxidants 4-CP UV, 254 nm. organic oxidants, PAA, PNBA, 4-CP, 51.4 mg/L (14)
MEKP
pH, 9.5
UV 4-CP 400 nm cut-off filter; temperature constant at – (33)
30 ± 0.2◦ C; visible light source, 250 W Xe
lamp; irradiance intensities of Vis of Xe
lamp; UV of mercury lamp were 40.9 and
480.0 W/cm2 .
UV/TiO2 4-CP pH, 5. Magnesium barium-doped TiO2 4-CP, 250 mg/L (34)
nanoparticles containing both anatase and (35)
rutile phases together, Mg2+ or Ba2+ metal

267
ion-doped nano-TiO2, anatase phase.
UV, 253.7 nm; pH, 3.5–9; ZnO, 1.0–3.0 g/L. 4-CP, 40–100 mg/L
optimum loading, 2.0 g/L
UV/catalyst 2, 4-DCP, 4-CP UV, 254 nm; pH, 7.0; reaction time,120 min; CP, 50–300 mg/L (36)
current density, 39 mA/cm2 ; distance H2 O2 , 8.3 mg/L
between electrodes, 2 cm; catalyst dosage,
200 mg.
UV/ozone 2,4-DCP,2-CP, 4-CP, pH, 6.2–6.5; ozonization time, 1 h; total 4-CP, 2,4-DCP, 6mg/L; (37)
2,4-DCP, 2,4,6-TCP, contact time up to 94 h. dissolved ozone in
2,3,4,6-TeCP, PCP UV, 254 nm; pH, 2.5, 9.5; ambient water, 7–40 mg/L; CP,
temperature. 51.4 mg/L (8)
UV/H2 O2 4-CP UV, 253.4 nm both acidic and basic media. 2-CP, 1500 mg/L (38)
H2 O2, ,516,2579,5158,
10316 mg/L.
268 S. Sharma et al.

(pH = 2.5). Conversion of 2-CP is much higher than the corresponding

TOC removal (8). In another report, the researchers (36) carried out work
using a carbon/polytetrafluoroethylene (C/PTFE) O2 -fed as the cathode and
Ti/IrO2 /RuO2 as the anode. The degradation of three organic compounds
(phenol, 4-CP and 2,4-DCP) is investigated in the diaphragm (diaphragm
material being terylene) electrolysis device by electrochemical oxidation pro-
cess (36). The 4-CP is effectively dechlorinated and rapidly oxidized in the
cathodic compartment (36). Mineralization in the cathodic compartment is
better than that in the anodic compartment (36). The authors note that the
dechlorination effect of 4-CP is better than that of 2,4-DCP (36).
The 2,4-DCP is more resistant towards O3 compared to 4–CP (37).
Longer reaction times/higher doses of ozone are needed for complete
mineralization (8, 37). After complete oxidation of CPs, high amounts of
chlorinated intermediates are noted to be left in the solution. However, the
chlorinated intermediates did not appear to increase the acute toxicity of
ozonated or O3 /UV treated CPs to a Daphnia magna 24-hour test (8). The
noteworthy aspect is that ozonation caused 90–95% reduction of CP levels,
and the ozonated samples possessed only minor/no adverse effects to the
aquatic test organism Daphnia magna (8). Several degradation intermediates
detected in the HPLC-chromatograms are detected within 5–10 minutes after
initiation of the treatment. Also, the change of colorless initial mixture to
pinkish/brownish indicates the formation of reaction intermediates with
aromatic structures. The concentration of intermediates, however, slowly
decreases during extended treatment time, and also the disappearance of the
mixture color towards the end of the oxidation demonstrates the destruction
of aromatic structures (8).
Increase in H2 O2 in solution leads to higher 2-CP conversion and TOC
removal (38). However, conversion is observed to remain unchanged on
varying its initial concentration (38). In their work on degradation of 4-CP
with organic oxidants, the authors (14) report PAA to be a better oxidant
than MEKP and PNBA. It is propounded that the haze in PNBA solution may
be the cause of interference in the oxidation/degradation process (14).
AOPs have thus emerged and evolved as potentially powerful tech-
niques in remediation of wastewaters as they facilitate degradation/
mineralization (29, 31, 39). This review further focuses on the main aspects
of CP degradation/mineralization by AOPs. A detailed comparison of pro-
cesses with respect to process conditions and degradation products formed
is presented in Table 2 (3, 8, 9, 14, 36, 40, 41). The noteworthy features of
the works presented in Table 2 are summarized in the following paragraphs.
The degradation/mineralization kinetics of 4-CP, with organic oxidants
in basic media is investigated by differential and integral methods (14). PAA
is found to degrade/mineralize 4-CP to the extent of 98%. The possible inter-
mediate compound is 1,4-benzoquinone (intermediate) and the final product
(GC-MS analysis) is identified as 4-methyl-3-penten-2-one (14). Maximum
 TABLE 2 Comparison of CP degradation processes with respect to process conditions and degradation products formed

Process conditions
Degradation
Target compounds Specific conditions pH /Temperature Concentration products/Intermediates Ref.

o-CP Oxygen partial pressure 100–200◦ C Fe, 100mg/L 100% o-chlorophenol (3)
of 0.3 MPa removal at 150◦ C in
150 min with FeSO4 as
catalyst.
4-CP, 2,4 DCP, 2,4,6 TCP, UV/H2 O2 pH, 2.5, 9.5 H2 O2, quinines (8)
2,3,4,6 Tetra-CP, PCP UV, 254 nm ambient temperature 13.57 mg/L
4-CP, PCP, 2,4-DCP, electro-Fenton method pH, 2.5 4-CP, 25mg/L; benzoquinone, 1, (9)
2,4,6-TCP 34.56 mg/L 4-catechol, 4-chloro-1,

269
dissolved O2 Na2 SO4, 19860 mg/L 2-catechol, phenol.
Na2 SO4, electrolyte.
4-CP UV, 254 nm pH, 9.5 4-CP, 51.4 mg/L 1, 4 benzoquinone (14)
H2 O2 /PAA/PNBA/MEKP ambient temperature. (intermediate)
4-methyl-3-penten
2-one
4-CP, 2,4-DCP OH∗ released by pH, 7.0 4-CP, 2,4-DCP, 100 mg/L 4-chlorocatechol, (36)
Ti/IrO2 /RuO2 anode benzoquinone, maleic,
(DSA), a self-made fumaric, oxalic and
C/PTFE O2 -fed formic acids.
cathode.
Reaction time, 120 min.
(Continued)
 TABLE 2 (Continued)

Process conditions
Degradation
Target compounds Specific conditions pH /Temperature Concentration products/Intermediates Ref.
◦
2-CP Ionic strength maintained pH 3. Temperature, 25 C 2-CP, 0.625 to 100 mg/L. 4-chloro-1,3-benzendiol; (40)
approximately constant 2-chloro-5-methyl-
at 0.1 N by the addition phenol;
of 50 mL of 2 N 2-chloro-6-methyl-
NaClO4 . 0, 10, 50, 100, phenol;
200, and 500 mg/L of 4-chloro-3-methyl-
H2 O2 and 0.5, 1, 2, 5, phenol;
and 10 mg/L of Fe2+2 2-chloro-p-hydro-

270
in 2-CP wastewater are quinone;
added 2-chloro-p-
benzoquinone; and
2,6-dichloro-2,
5-cyclohexadiene-1,
4-dione
4-CP UV, 369, 435 nm pH, 4,7,10 25.7 mg/L 2,3-dihydroxybenzoic (41)
catalyst dosage, pH, 4,7,10 25.7 mg/L acid,
1.2 g/L; 2,5-dihydroxybenzoic
TiO2 , WO3 , SnO2 , acid, catechol
TiO2 /WO3 and
TiO2 /SnO2 systems
 Chlorophenol Remediation in Wastewater 271

COD removal within 6 minutes is reported (14). The investigation

reports complete CP degradation supported by 100% COD removal
(150 minutes) (3). Slow formation of inorganic chloride ions and quinines as
by-products is also reported (8). Both hydroxylation and cathode reductive
dechlorination mechanism are proposed for Cl− ion release.
Benzoquinone, 1, 4-catechol, 4-chloro-1, 2-catechol, phenol are the
degradation compounds formed (9). In TiO2 /WO3 system, the degradation
efficiency increases significantly as compared to a single TiO2 or WO3 sys-
tem at 435 nm. TiO2 /WO3 degradation of 4-CP is reported to be inhibited at
369 nm (40). The intermediates/degradation products include 4-chloro-1,3-
benzendiol; 2-chloro-5-methyl-phenol; 2-chloro-6-methyl-phenol; 4-chloro-
3-methyl-phenol; 2-chloro-p-hydro-quinone; 2-chloro-p-benzoquinone; and
2,6-dichloro-2, 5-cyclohexadiene-1,4-dione. In the TiO2 /SnO2 system, the
degradation efficiency at 369 nm increases at 435 nm as compared to
the single TiO2 /SnO2 system. The degradation products/intermediates are
2,3-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid and catechol (41).
A 90% COD decrease (120 minutes) is observed and 4-chlorocatechol,
benzoquinone, maleic, fumaric, oxalic and formic acids are reported to be
formed (36).
From the ensuing literature survey, it can be concluded that the var-
ious AOPs have emerged and evolved as potentially powerful techniques
for wastewater containing recalcitrant, inhibitory and toxic compounds with
low biodegradability (29, 40–49). Chemical oxidation of organic pollu-
tants based on ultrasound (40), and also with hydrogen peroxide/goethite
(50), is an emerging technology in treating wastewaters containing organic
pollutants.
Lin and Ma (40) reported more than 99% of 2-CP decomposition
and 86% of 2-CP mineralization using the ultrasound/Fe2+ /H2 O2 process
at Fe2+ of 10 mg/L and H2 O2 of 500 mg/L. A slight increase in the
oxidation-reduction potential (ORP) values with increasing Fe2+ dosages,
and an apparent increase with increasing H2 O2 dosages are observed.
The major intermediate formed during the decomposition of 2-CP, 2-
chloro-p-benzoquinone, is also readily decomposed. Lu (50) opined that
since Fe2+ and Fe3+ create a better oxidation efficiency in the presence
of goethite and hydrogen peroxide as compared to Fenton system, the
ultrasound/Fe2+ /H2 O2 method is a more promising and effective method
than the ultrasound/Fenton method for the decomposition of 2-CP.
Results (50) indicate that 2-CP is decomposed with hydrogen perox-
ide catalyzed by goethite and the oxidation rate increases with decreasing
goethite particle size. The 2-CP degradation is retarded with 0.8 g/L of
goethite as ferrous ions are not produced at this condition. Comparing the
oxidation of 2-CP, 4-CP, 2,4-DCP, it is observed that 2-CP is oxidized easily
than the other two. Within 4 hours, 2-CP disappears completely, but only
14.4% of 2,4-DCP is degraded. The main mechanism of goethite catalyzing
272 S. Sharma et al.

hydrogen peroxide to oxidize 2-CP is attributed to the catalysis of ferrous

ions and goethite surface (50).
The variety on AOPs is attributed to the numerous ways for hydroxyl
radical production. Considering the different possible ways of hydroxyl radi-
cal production, nonphotolytic and photolytic processes are differentiated and
discussed in detail as follows:

Nonphotolytic Degradation by Electro-Fenton Technique

The electro-Fenton approach consists of either adding ferrous iron or
reducing ferric iron electrochemically with the simultaneous production of
hydrogen peroxide upon the reduction of oxygen on several electrodes
(mercury pool, vitreous carbon or carbon-polytetrafluoroethylene O2 fed
cathodes) (51). Comparison of treatment methods of various CPs by electro-
Fenton method and relationship between chlorine content and degradation
is studied using the electrochemical method (36). Degradation kinetics with
various CPs is compared by Fenton’s reagent, photolysis O3, sonolysis and
different degradation sequences (52, 53). 4-CP, 2, 4-DCP, 2, 4, 6-TCP and
PCP are degraded by electro-Fenton method. Special attention is paid to the
relationship between chlorine content and degradation rate.
Combined process of reduction and oxidation improves 4-CP degrada-
tion efficiency. According to the authors (9), both hydroxylation and cathode
reductive dechlorination take place for Cl_ ion release. The degradation pro-
cess decreases with the increase of chlorine content with exception of 4-CP
(9). Degradation and kinetics of CPs wastewater by ozone-hydrogen perox-
ide is investigated (54). The effects of different operating conditions, such as
various reactant concentrations, various ratios of H2 O2 to O3 and various pH
values in solutions, on oxidation reaction is explored.

Direct Photolysis
Direct photolysis involves the interaction of light with molecules, in addition
to water, to bring about their dissociation to intermediates (25). In the pho-
tochemical reactions, the main step is the generation of hydroxyl radical by
photolysis (55). Photocatalytic processes have shown higher half-reaction
times than the rest of the AOPs in the treatment of most of CPs (25).
The advantage, with respect to the other AOPs, is that no oxidant is con-
sumed during the oxidation and no further separation is required after the
reaction (25).

UV/H2 O2
Hydrogen peroxide, H2 O2 , is a benign and safe oxidant which is very widely
used. Synergy is best exhibited when it is used in combination with UV
(25). UV/H2 O2 is found efficient in the degradation of 2, 4-DCP and other
 Chlorophenol Remediation in Wastewater 273

chlorophenols removal (56). A comparison between DCP degradation rate in

alkaline conditions and direct UV (20-W 254 nm lamps) irradiation is made
and reported that the addition of hydrogen peroxide at acidic pH increases
the reaction rate by one order of magnitude (56). The rate of reaction is
found to be pH dependent and increases when alkaline conditions are used.
This is probably because at 253.7 nm, the anions peroxide HO2– has higher
molar absorption coefficient (18.6 M−1 cm−1 ) (26).

VACUUM UV
Vacuum ultraviolet (VUV) photochemical processes use excimer light sources
emitting in this domain (29). It is found to be an efficient method for complete
photo mineralization of DCP (57) and the degradation of organic pollutants in
liquid or gaseous phase by the production of effective hydroxyl radicals (58).

UV/OZONE
The treatment with ozone is enhanced by use of UV radiation (254 nm)
as it generates more hydroxyl radicals (59). The extinction coefficient of
O3 at 254 nm (3300 M−1 .cm−1 ) is very superior to that of H2 O2 (31). The
study comprises of the ozonation of several CPs in alkali media and reveals
that the degradation curves are nearly same for all CPs. Pseudo–first-order
kinetic constants and half-life times also confirmed the small differences in
the removal of the CPs at this pH (60). It is reported that the rate of disap-
pearance of PCP is very similar between pH 7–12. When the ozonation is
carried out in acidic media (pH ≈ 2) the decomposition of ozone, which is
initiated by the action of HO− ions (61), is too low and consequently the for-
mation of hydroxyl radicals is limited. According to this, the main pathway in
the degradation of CPs is the direct ozonation, which is a selective reaction
with quite slow kinetic constants, which lies in the range of 1–1000 M−1 s−1 .
It is opined (8) that an increase in the number of chlorine atoms in the
aromatic ring provides an increase in the degradation rate, since the presence
of chlorine enhances the dechlorination step, and therefore, the degradation
is faster. This statement is in good confirmation with the results obtained
(59). Results also indicate that at higher pH, the degradation of CPs is high.
Similar results are reported for ozonation of 2-CP, 4-CP and 2,4-DCP at pH
6 and 9 (62). After 10 minutes of reaction at pH 6 the degradation of 2,4-DCP,
4-CP and 2-CP are 79.2, 63.9 and 34.3%, respectively. Studies regarding DCP
removal by the O3 /UV process (62–64) by different ozone combinations are
also reported.

Combining Processes
The photodegradation of CPs by ozone and UV radiation, alone or com-
bined with hydrogen peroxide or ferrous and ferric ions, is also reported
274 S. Sharma et al.

(65–71). Several authors have compared the O3 /UV system with the direct
photolysis or simple ozonation. Some authors (59–62, 65–67) conclude that
the combination O3 /UV improves the efficiency of the single processes. The
destruction of 2-CP, 4-CP and 2,4-DCP by combination of photolysis and
ozonation, direct photolysis and ozonation alone is compared (62, 65). It is
concluded that the synergistic effects of the combined procedure increase
with increasing initial pH of solution to basic levels. This fact is ascribed
to the fact that the initiation of ozonation is catalyzed by OH− ions. The
experimental results also prove that the potentialities of photolytic ozonation
compared to direct photolysis and ozonation alone are remarkable for the
treatment of industrial wastewaters containing CPs.
The degradation of CPs by the combined process UV/O3 at 25◦ C and
pH 2 is studied (68). When comparing the ozonation results with single pho-
todecomposition at pH 2, it is found that the combined system accelerates
the decomposition with an extremely high rate constant for 4-CP. The other
CPs studied (2,4-DCP, 2,4,6-TCP and 2,3,4,6-TeCP) present a slight increase
in the rate constants when the substituent chlorine atoms increase (same
sequence observed in single ozonation). The mineralization of 4-CP is more
effective when subjected to photolytic ozonation. The degradation of 4-CP,
2-CP, 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TeCP and PCP is studied by several AOPs
(8). Despite the fact that the molar absorptivity of CPs in known to be rel-
atively high in the UV region, the combination of UV with ozone does not
accelerate the degradation of CPs further (8).

UV/FENTON
The addition of an iron ion (Fe3+ /Fe2+ ) is reported to accelerate the
UV-enhanced ozonation of several pollutants (23, 51, 68–72). Under the
conditions of UV irradiation, the photolysis allows the regeneration of
the Fe2+ by means of Fe3+ complexes (62). Fenton process is used for
the degradation of 4-CP, and 2,4-DCP (73). The stoichiometric coefficient
for Fenton reaction is approximately 0.5 mol of organic compound/mol
H2 O2 . The process is found to eliminate toxic substances and increases
the biodegradability of the treated water (74). Comparing the degradation
of DCP by Fenton and photo-Fenton process, the authors (74) noted that
during Fenton reaction only a small abatement of DCP is observed whereas
78% mineralization is achieved by the photo-Fenton process. As reported
by several authors (52, 53, 75), the degradation and dechlorination of CPs
by Fenton’s reagent follows pseudo–first-order kinetics. Significantly, this is
achieved with a H2 O2 dose of 50–75% of the stoichiometry (76). However,
small chlorinated alkanes, n-paraffins and short-chain carboxylic acids are
noted to show resistance to oxidation (61). CP degradation by different AOPs
is reported (51). The O3 /UV/Fe (II) system is found to be the most effective
method, achieving complete mineralization in a few minutes. Complete
 Chlorophenol Remediation in Wastewater 275

mineralization of DCP among other chlorophenols achieved by O3 /UV/Fe

(III) is reported (51).
An experimental study (77) on 4-CP degradation with H2 O2 by AOP,
photo-Fenton type, is reported. The oxidation process is determined by
the very high oxidative potential of the OH∗ radicals generated inside
the reaction medium by Fe2+ catalyst coupled with UV radiation. The
influence of excess H2 O2 , initial solution pH, Fe2+ catalyst concentration,
initial concentration of 4-CP and reaction time on the oxidation process is
reported (77).
The Cr(VI)/H2 O2 system is proposed as a viable AOP (78). The oxida-
tion of organic compounds in water is investigated (78) using chromate as an
activator of H2 O2 . The 4-CP degradation is successfully achieved at circum-
neutral pH. Unlike the traditional Fenton-based activation of H2 O2 , that is
mainly limited to acidic condition, the oxidative capacity of the proposed
Cr(VI)/H2 O2 system is active over a wide range of pH 3–11. H2 O2 substi-
tutes the oxo-ligands of chromate by the peroxo-ligands, and subsequently,
converts chromate(VI) into a tetraperoxochromate(V) complex. The instan-
taneous disproportionation between chromium-coordinated peroxo-ligands
initiates the generation of HO∗ that are responsible for the degradation of
organic compounds in the Cr(VI)/H2 O2 system. The oxidation rate of 4-
CP and the in situ generated concentration of peroxochromate(V) decreases
with increasing pH. The oxidation of 4-CP investigated at different H2 O2
concentrations and pH indicates the pH-dependent competition between
peroxo-ligand exchange and dissociation reactions.
Bokare and Wonyong (79) also proposed Cr(III)/H2 O2 combined with
Cr(VI)/H2 O2 process as a viable AOP operating over a wide pH range using
the reusable redox cycle of Cr(III) and Cr(VI). The Fenton-like oxidation
of 4-CP is initiated by the reaction between the aquo-complex of Cr(III)
and H2 O2 , which generates HO∗ during the stepwise oxidation of Cr(III) to
Cr(VI). The Cr(III)/H2 O2 system is inactive in acidic condition, but exhibits
maximum oxidative capacity at neutral and near-alkaline pH. Because Cr(VI)
is reported (63) to activate H2 O2 to efficiently generate HO∗ , the dual role
of H2 O2 as an oxidant of Cr(III) and a reductant of Cr(VI) is utilized to
establish a redox cycle of Cr(III)-Cr(VI)-Cr(III). The oxidation rate of 4-CP
in the Cr(III)/H2 O2 solution is highly influenced by pH, which is ascribed
to the hydrolysis of CrIII (H2 O)n into CrIII (H2 O)n-m (OH)m and the subsequent
condensation to oligomers (79). From ongoing discussion, it is concluded
that CPs can be degraded at quite significant rates by all the methods studied.

HETEROGENEOUS CATALYSIS
Use of photocatalytic semiconductors is investigated for the destruction of
several CPs in water, including TiO2 , cadmium sulphide, ZnS and active
carbon (72, 80–83). It is reported that TiO2 offers advantages of its low cost,
276 S. Sharma et al.

stable nature and high photo-activity when exposed to near-UV light (72,
84–86). The experimental results obtained (87) are in confirmation for DCP,
TCP and PCP degradation by heterogeneous photocatalysis using TiO2. It
is reported that cadmium sulfide has a higher rate constant than TiO2 for
the degradation of 2-CP (88). The photocatalytic degradation of 2,4,6-TCP,
2,3-dichlorophenol, 2-CP and 2,4-DCP on aqueous suspensions of α-Fe2 O3
and α-FeOOH and TiO2 is studied. α-FeOOH is found to be inactive for CPs
degradation with an exception of 2,4-DCP where a modest effect is observed.
Total mineralization of CPs is observed on TiO2 while partial mineralization
is noted on Fe2 O3 . The results of the solar degradation of 2-CP and 2,4-DCP
in the presence of TiO2 and Na4 W10 O32 show that the degradation of the
pollutants is twice as fast in the presence of TiO2 . Total degradation at near
ambient temperature is also reported (42).
Experimental studies report that the 2-CP photodegradation rate
increases when they are saturated by oxygen and metallic ions such as Ag+ ,
Cr2 O7 2− , Cu2+ and Fe2+ (86, 89). The photocatalytic degradation of 2-CP,
2,4-DCP and 2,4,6-TCP in the presence of manganese ions at pH 3 is stud-
ied (90). The results indicate that dissolved manganese ions can increase
the rate of CPs oxidation in the TiO2 photocatalytic system. DCP complete
mineralization is achieved during photocatalysis process with TiO2 and 6-W
254 nm Hg lamp (91). The photocatalytic treatment of DCP by using TiO2
and solar light reveals that reaction is first order with respect to DCP concen-
tration (59). Out of the many catalysts employed for degradation, TiO2 in the
anatase form is found to possess interesting features, such as high stability,
good performance and low cost (31). Degradation of CPs by photocatalysis
consists of use of coupled semiconductors (92, 93). The enhancement of
photo degradation efficiency of 2-CP in TiO2 /cadium sulphide/UV system
is attributed to the rapid transfer of the photogenerated electrons from the
cadmium sulfide to TiO2 (93).
Satuf et al. (94) employed intrinsic kinetic expressions, previously
obtained in a laboratory reactor, to predict the performance of a bench scale
reactor of different configuration/operating conditions for 4-CP degradation.
Good agreement is found between simulation and experimental data. The
root mean square error of the estimations is 9.9%. The photocatalytic pro-
cess is reported to enhance the biodegradability of the reacting mixture, and
the initial toxicity of the pollutant is significantly reduced by the treatment.
Photocatalysis employing TiO2 is a useful method to degrade a wide variety
of organic and inorganic pollutants from water and air. However, the appli-
cation of this AOP at industrial scale requires development of mathematical
models to design and scale-up photocatalytic reactors.

UV/ORGANIC OXIDANTS
PAA is reportedly used in the oxidative degradation of a highly halogenated
porphyrin as tetrakis (11) in the degradation of 1-methylnaphthalene in lake
 Chlorophenol Remediation in Wastewater 277

sediments (12), for the treatment of polycyclic aromatic hydrocarbon (PAH)

contaminated soils (13) and in 4-CP degradation (14). The use of UV, 254 nm
and organic oxidants PAA, PNBA and MEKP is reported for 4-CP degradation
in basic media (14). Fractional order of reaction is achieved by differential
method of analysis. First-order dynamics is approximated for 4-CP degrada-
tion by organic oxidants for initial reaction time (45 seconds) and the rate
parameters are either first- or second-order for different oxidants for the
remaining time period.
The data obtained with UV/PAA, UV/PNBA and MEKP oxidants are
fitting well with both first- and second-order kinetics; for MEKP first-order
dynamics is more suitable. Oxidation data with PAA and PNBA are not fitting
well to both the rate equations. The results for UV/MEKP are not satisfac-
tory with both the kinetic models and the authors attribute the same to the
formation of some intermediate compounds having same retention time and
overlapping of the concentration. Concentration of 4-CP is found to reduce
and thus 98% degradation of 4-CP with no trace of PAA is observed. GC-MS
analysis results confirm mineralization of 4-CP (14).
At this juncture, the information regarding mechanism of CP degradation
and the kinetic aspects assumes considerable significance. The following sec-
tion addresses CP degradation kinetics by various schemes with due regard
to the parameters employed therein.

MECHANISM AND KINETIC STUDY

The kinetics and mechanism of CP degradation in the natural environment

is a superposition of reactions depending on experimental conditions such
as the wavelength of irradiation, pH of solution, concentration (78). AOPs
have their own kinetics and mechanisms for oxidizing organic compounds
depending on irradiation source characteristics, physical and geometri-
cal characteristics of the reactor and the type and the dose of reagents
functioning in the reactor (95).
This discussion is further extended to the study of various schemes
employed for CP degradation with respect to oxidants, catalysts, lamps used
along with specific operating conditions and the rate constants achieved
thereof are also presented. Comparison of various processes of CP degrada-
tion like direct UV-photolysis (6, 8,10, 62, 71, 95); UV/H2 O2 reagent (8, 10,
71); O3 /UV reagent (10, 62, 65); photocatalysis (23, 27, 42, 83, 96–98); Fenton
reagent (52, 95, 99–101); UV/organic oxidants (11, 14); nonphotocatalytic by
ozone reagent (10, 62, 65) with respect to specific operating conditions and
the rate constants achieved are presented in Tables 3a-g.
According to the literature survey, it is obvious that AOPs based on H2 O2
(Fenton, photo-Fenton and H2 O2 -UV) achieve CP degradation in a short
period of time. These techniques are frequently employed by researchers
as they are less costly than ozonation. Photolytic method is advantageous
 TABLE 3 Chlorophenol degradation by ultraviolet photolysis and other methods

Radiation
Chlorophenol intensity
Pollutant [Cpo ] mM pH Temperature ◦ C λ nm Einstein−1 s−1 KCp min−1 Ref.

Direct UV Photolysis
2-CP 0.78 6.0, 9.0 room 320–400 – 1.52 × 10−3 , (62)
9.00 × 10−4
2-CP 0.40 2.5 room 250 6.45E-07 8.76 × 10−3 , (8)
4.04 × 10−2
4-CP 0.78 6.0, 9.0 room 320–400 5.97 × 10−5 9.32 × 10−3 , (62)
5.10 × 10−4
4-CP 0.40 2.5, 9.5 room 250 6.45E–07 2.52 × 10−2 , (8)
5.08 × 10−2
4-CP 0.3 2.0, 9.0 25 185–436 4.80 × 10−4 0.539, 0.432 (95)

278
3.52 × 10−5
4-CP 0.30 2.0 room 185–436 4.80 × 10−4 0.564 (10)
2,4-DCP 0.78 6.0, 9.0 room 320–400 5.97 × 10−5 5.90 × 10−4 , (62)
7.00 × 10−4
2,4-DCP 0.40 2.5, 9.5 room 250 6.45E-07 6.95 × 10−3 , (8)
4.98 × 10−2
2,4-DCP 0.30 2.0 room 185–436 4.80E-04 3.80 × 10−2 (10)
2,4,6-TCP 0.40 2.5, 9.5 room 250 6.45E-07 9.48 × 10−3 , (8)
2.03 × 10−2
2,4,6-TCP 0.30 2.0 room 185–436 4.80E-04 2.60 × 10−2 (6)
2,4,6-TCP 0.30 2.0 25 185–436 4.80E-04 2.60 × 10−2 (71)
2,3.4,6-TTCP 0.30 2.0 room 185–436 4.80E-04 2.10 × 10−2 (10)
PCP 0.04 2.5, 9.5 room 250 6.45E–07 8.16 × 10−2 , (8)
5.39 × 10−2
 TABLE 3 (Continued)

Radiation
Chlorophenol intensity
Pollutant [Cpo ] mM [H2 O2 ] mM pH Temp ◦ C λ nm Einstein−1 s−1 KCp min−1 Ref.

Degradation by UV/H2 O2 Association

2-CP 0.40 40 2.5, 9.5 room 250 6.45E-07 5.07 × 10−2 , (8)
5.11 × 10−2
4-CP 0.40 40 2.5, 9.5 room 250 6.45E-07 5.07 × 10−2 ; (8)
5.11 × 10−2
4-CP 0.30 0.50 2.0 25 185–436 3.52E-05 0.549 (71)

279
4-CP 0.30 0.50 2.0 room 185–436 3.52E-05 0.601 (10)
2,4-DCP 0.40 40 2.5, 9.5 room 250 6.45E-07 8.64 × 10−2 (8)
5.22 × 10−2
2,4-DCP 0.30 0.50 2.0 25 185–436 4.80E-04 2.54 × 10−2 (71)
2,4-DCP 0.30 0.50 2.0 room 185–436 4.80E-04 4.40 × 10−2 (10)
2,4,6-TCP 0.40 40 2.5, 9.5 room 250 6.45E-07 0.109, 5.46E-07 (8)
2,4,6-TCP 0.30 0.50 2.0 25 185–436 4.80E-04 1.80 × 10−2 (71)
2,4,6-TCP 0.30 0.50 2.0 room 185–436 4.80E-04 3.30 × 10−2 (10)
2,3.4,6-TTCP 0.30 0.50 2.0 25 185–436 4.80E–04 2.90 × 10−2 (71)
PCP 0.40 40 2.5, 9.5 room 250 6.45E–07 0.458, 0.267 (8)
 TABLE 3 (Continued)

Radiation
Chlorophenol intensity
Pollutant [Cpo ] mM Oxidant pH λ nm Einstein−1 s−1 KCp min−1 Ref.

Degradation by Ozone/UV Reagent

2-CP 0.78 O3 feed flow rate (mg 6.0 320–400 5.97 × 10−5 7.68 × 10−3 (62)
min−1 ) = 5.0
2-CP 0.18 O3 feed flow rate (mg 3.4 – 2.50 × 10−5 – (65)
min−1 ) = 8.3
4-CP 0.78 – 6.0 320–400 5.97 × 10−5 1.18 × 10−2 (62)

280
4-CP 0.30 – 2.0 185–436 1.76 × 10−5 – (10)
2,4-DCP 0.78 O3 feed flow rate (mg 6.0 320–400 5.97 × 10−5 8.59 × 10−3 (62)
min−1 ) = 5.0
2,4-DCP 0.30 – 2.0 185–436 1.76 × 10−5 6.5 × 10−2 (10)
2,4-DCP 0.78 O3 feed flow rate (mg 6.0 – – 3.67 × 10−3 (62)
min−1 ) = 5.0
2,4,6-TCP 0.30 2.0 185–436 1.76 × 10−5 6.80 × 10−2 (10)
2,4,6-TCP 0.18 O3 feed flow rate (mg 3.4 – 2.5 × 10−5 – (65)
min−1 ) = 8.3
 TABLE 3 (Continued)

Chlorophenol Pollutant [Cpo ]mM Oxidant pH Temperature ◦ C KCp min−1 Ref.

Degradation by Fenton’s Reagent

2-CP 0.50 [H2 O2 ] = 5.0 mM; 3.5 room 1.67 (52)
[Fe2+ ] = 0.20 mM
2-CP 0.39 [H2 O2 ] = 2.2 mM; 3.0 30 1.92 × 10−2 (101)
[Fe2+ ] = 0.008 mM
4-CP 10.0 [H2 O2 ] = 30 mM; 3.5 room – (99)
[Fe2+ ] = 0.005 mM
4-CP 2.00 [H2 O2 ] = 6.0 mM; 3.0 20 1.55 (100)

281
[Fe2+ ] = 0.3 mM
2,4-DCP 0.50 [H2 O2 ] = 5.0 mM; 3.5 room 0.995 (52)
[Fe2+ ] = 0.20 mM
2,4-DCP 0.30 [H2 O2 ] = 0.5 mM; 2.0 25 7.00 × 10−4 (95)
[Fe2+ ] = 0.010 mM
2,4,6-TCP 0.50 [H2 O2 ] = 5.0 mM; 3.5 room 0.15 (52)
[Fe2+ ] = 0.20 mM
PCP 0.80 [H2 O2 ] = 4.0 mM; 2.0 25 – (100)
[Fe2+ ] = 0.020 mM
 TABLE 3 (Continued)

Chlorophenol Pollutant [Cpo ] mM pH Catalyst Lamp KCp min−1 Ref.

Degradation by Photocatalysis
2-CP 0.78 2.5 TiO2 (2.0g/L) 100 W high pressure Hg lamp 3.89 × 10−6 (42)
2-CP 0.078 2.5 TiO2 (2.0g/L) 15 W high pressure Hg lamp 2.10 × 10−6 (23)
2-CP 0.78 2.5 TiO2 600 W high pressure Hg lamp 9.10 × 10−6 (98)
4-CP 1.00 – TiO2 TiO2 /AC- 125 W high pressure Hg lamp 2.70 × 10−4 (96)
MTiO2 /AC-PC 6.40 × 10−4
5.24 × 10−4

282
4-CP 1.00 – TiO2 TiO2 /AC- 125 W high pressure Hg lamp 2.70 × 10−4 (96)
MTiO2 /AC-PC 6.40 × 10−4
2.7 × 10−4
2,4,6-TCP 1.0 1.0 PW12 O40 3- Oriel 1000 W Xe arc lamp 7.50 × 10−5 (97)
2,4,6-TCP 0.50 6.0 α-Fe2 O3 (1.5g/L) 125 high pressure Hg lamp 1.17 × 10−6 (98)
2,4-DCP 0.12 6.0 TiO2 (0.1 g/L) 125 W high pressure Hg lamp 4.03 × 10−6 (27)
2,4-DCP 0.34 6.6 TiO2 (1 g/L) solar light in flat reactor 2.82 × 10−7 (83)
PCP 0.65 7.0 TiO2 (0.1 g/L) 125 W high pressure Hg lamp 2.96 × 10−6 (27)s
 TABLE 3 (Continued)

Chlorophenol Pollutant [Cpo ] mM Oxidant pH Temperature ◦ C λ nm KCp min−1 Ref.

Degradation by UV/Organic Oxidants

4-CP 0.4 PAA 9.5 room 254 0.029 s−1 (14)
PNBA 0.019 s−1
MEKP 0.011 s−1
Fe(F20 TPP) Cl (tetrakis) 0.0094 PAA acidic 25–45 190–1100 1.18 × 104 (11)

Chlorophenol Pollutant [Cpo ]mM Oxidant pH KCp min−1 KO3 min−1 Ref.

Degradation by Ozone Alone

2-CP 0.78 O3 feed flow rate 6.0 1.49 × 10−3 – (62)
(mg min−1 ) = 5.0
4-CP 0.78 – 6.0 2.3 × 10−3 – (62)
4-CP 0.30 – 2.0, 9.0 1.7 × 10−2 – (10)

283
0.239
4-CP 0.18 O3 feed flow rate 3.4 – – (65)
(mg min−1 ) = 8.3
2,4-DCP 0.30 – 2.0, 9.0 – 2.4 × 10−2 , (10)
0.315
2,4-DCP 0.18 O3 feed flow rate 3.4 – – (65)
(mg min−1 ) = 8.3
2,4,6-TCP 0.30 – 2.0, 9.0 4.40 × 10−2 , (10)
0.314
2,4,6-TCP 0.18 O3 feed flow rate 3.4 – – (65)
(mg min−1 ) = 8.3
2,3.4,6-TTCP 0.30 – 2.0, 9.0 – 9.40 × 10−2 , (10)
0.415

CP: chlorophenol; AC: acetic acid; PAA: peroxyacetic acid; PNBA: paranitrobenzoic acid; MEKP: methyl ethyl ketone peroxide.
284 S. Sharma et al.

with respect to the other AOPs, since no oxidant is consumed during the
oxidation and no further separation is required after the reaction (Fe2+ ions
in the case of Fenton-like processes during the reaction). The O3 /UV and
photo-Fenton combination techniques are reported to achieve high reac-
tion kinetic rates for degradation of TTCPs. Photo-Fenton is found suitable
for the treatment of DCP, using single ozonation and Fenton. The lowest
half-times are reported for the degradation of MCPs, TCPs and TTCPs when
single ozonation is employed. From the data presented in Tables 3a-g, sin-
gle ozonation appears to be the most suitable method for the treatment of
aqueous solutions containing CPs. Although the use of UV/organic oxidant
gives promising results (11, 14),it is less in vogue.
At this juncture, it is imperative to impart due significance to the modes
of operation of processes employed in CP degradation. Consequently the
following section is devoted to the discussion of reactor configuration and
the mode of operation employed in CP degradation.

MODE OF OPERATION

A review of the available data reveals that batch, semi-batch and continuous
reactors are employed for CP degradation by AOPs. An important drawback
of AOPs is reported to be their high operational costs (47, 99-–02). It is
to be noted that completely mixed batch cylindrical glass vessels are the
most popular reactor configurations for the studies of degradation of CPs.
A summary is depicted in Table 4 (1, 8, 10, 50, 52, 53, 59, 62, 63, 65, 72–75,
85–87, 92, 100–111).
Among the different configurations, the lamp located in an axial posi-
tion housed by a sleeve (71), is the most widely used experimental setup
(Figure 1). Different radiation sources, high, medium and low-pressure mer-
cury vapor lamp for the generation of UV radiation (59, 71, 99, 100, 103,
106) and solar-simulated xenon lamps as a source of visible radiation (108,
112) are widely used for direct UV-photolysis and for techniques based on
UV/H2 O2 , UV/O3 , photo-Fenton’s reagents and photocatalysis.
A review of different investigations (Table 2) indicates that UV-coupled
oxidation can decompose several organic contaminants partially or totally
into less toxic and more biodegradable substances (113). Despite the fact
that AOPs facilitate the conversion of contaminants to less harmful com-
pounds, as oxygenated organic products and low molecular acids (114, 115)
(Table 2) they are limited to treatment of wastewaters containing low concen-
trations of organic or inorganic scavenging material (26). AOPs are applied
to complete the final mineralization of the organic matter (116–119) as a
polishing, pretreatment/post-treatment step (120, 121), depending on the
concentrations of the compounds followed by lesser expensive biological
processes (121).
 Chlorophenol Remediation in Wastewater 285

TABLE 4 Reactor configurations for various advanced oxidation processes (AOP) employed
in CP degradation

AOP Reactor configuration Mode of operation Ref.

Nonphotolytic
ozonation stirred reactors-glass bottles semi-batch 1, 8, 52, 59, 62,
or cylindrical vessel, 63, 65, 110, 111
bubble columns,
wetted-sphere adsorbers
Photolytic
direct photolysis/ cylindrical glass vessels batch 10, 50, 59, 75,
H2 O2 erlenmeyers or cylindrical 100, 103–106,
glass flasks 112
Photo-Fenton tubular configurations batch 106, 112
Photocatalysis cylindrical flasks or vessels, batch continuous 72, 5385–87, 92,
glass dishes, and annular 101, 102,
differential photo-reactors 107–109
rotating disk
photo-catalytic reactor
compound parabolic
collectors (CPC)
connected in series

Quartz tube

UV Lamp

Glass Reactor

FIGURE 1 Experimental setup of UV reactor.

286 S. Sharma et al.

Only a few installations are in operation today because of their high

operating costs on large-scale installations (93). AOPs, through the use of
cheap oxidants, have been demonstrated as a viable alternative for remov-
ing trace CPs. Ozone and hydrogen peroxide are the most diffused oxidants.
Ozone can react selectively, as an oxidant in its molecular form (O3 ), thus
leading to typical ozonation reactions with double bonds, amines, and phe-
nol derivatives, or non selectively, after formation of HO∗ . The synergistic
use of ozone with other oxidants (e.g., H2 O2 ) or in association with physical
means such as UV radiation is justified to reduce the selectivity of action in
the hope of amplifying the degradation of chlorophenols. The use of UV radi-
ation is energy-intensive, as doses required for the degradation can exceed,
by orders of magnitude (30 mJ/cm2 ), the amount needed for disinfection
processes, which never exceeds 1 mJ/cm2 . UV photolysis is investigated
(122) for typical disinfection operations and 50–80% removal of the target
compounds is obtained after application of radiation intensities exceeding
the equivalent necessary for 2 orders of magnitude (122).
UV photolysis enhanced (catalyzed) by the presence of TiO2 (anatase)
or ferrous ions (photo-assisted Fenton: Fe2+ /H2 O2 /UV) (123) are typical
examples. Other metal derivatives such as manganese dioxide and ferrate
ions can be used, alone and/or photo-assisted by UV radiation, because
of their high oxidation potentials (124). As mentioned, the Fenton process
is based on the use of ferrous ions in association with hydrogen peroxide
in acidic media (pH 3). Although the oxidation potential of ferrate ions is
greater than that of ozone, the acidic conditions of operation strongly limit
its use in full-scale installations (125). Formation of oxidation byproducts
after the application of different oxidants is not always sufficiently high-
lighted in the literature, and this can pose a real challenge to their extensive
application.

CONCLUSIONS

A review of CPs degradation methods reveals that the AOPs are proven
to be efficient treatment methods for degrading wastewaters containing
recalcitrant, inhibitory, and toxic compounds with low biodegradability.
The achieved detoxification of treated compounds supports the use of
AOPs to improve the capacity of conventional biological treatment to
remove toxic and poorly biodegradable substances. AOPs play a signifi-
cant role in enhancing the biodegradability of the wastewaters. The role
of AOPs in CP degradation is thus indispensable. A review of different
investigations of AOP based CP degradation methods reveals that AOPs
facilitate the conversion of contaminants to less critical compounds, and
the degradation yields environmentally acceptable products such as halide
ions, carbon dioxide and simple organic acids, which are approved as
 Chlorophenol Remediation in Wastewater 287

less toxic and more biodegradable compounds compared with the original
contaminants.
However AOPs are limited to treating waters which contain low concen-
trations of organic or inorganic scavenging material. Since no single method
can be singled out for efficient cost-effective degradation/mineralization of
CPs, it is important to develop newer techniques/adapt cost-effective strate-
gies as a combination of two or more sequential techniques to facilitate
complete CP degradation/mineralization. An ideal wastewater treatment pro-
cess is expected to completely mineralize all the toxic species present in the
waste stream without leaving behind any hazardous residues; it should also
be cost effective. Integration of treatment processes can be explored to reap
advantages of the methods employed and to minimize the drawback of each
method. Intensification of AOPs is one of the challenges for researchers in
this area.

ABBREVIATIONS

AOPs Advanced oxidation processes

CP Chlorophenol
CPCB Central Pollution Control Board
o-CP, 2-CP Ortho-chlorophenol, 2-chlorophenol
p-CP Para-chlorophenol
4-CP 4-chlorophenol
COD Chemical oxygen demand
2,3-DCP 2,3-dichlorophenol
2,4-DCP 2,4-dichchlorophenol
GC-MS Gas chromatography mass spectroscopy
HPLC High pressure liquid chromatography
2-MCP 2-mono chlorophenol
MEKP Methyl ethyl ketone peroxide
mg/L Milligrams per litre
OH∗ Hydroxyl radicals
ORP Oxidation-reduction potential
PAA Peroxyacetic acid
PAH Polycyclic aromatic hydrocarbon
PCP Pentachlorophenol
PNBA Para-nitro benzoic acid
ppm Parts per million
2,3,4,6-TeCP 2,3,4,6-tetrachlorophenol
2,4,6-TCP 2,4,6-trichlorophenol
TOC Total organic carbon
UV Ultraviolet
VUV Vacuum ultraviolet
288 S. Sharma et al.

REFERENCES

1. Ahlborg, U.B. and Thunberg, T.M. (1980) Chlorinated phenols: occurrence,

toxicity, metabolism and environmental impact. CRC Crit. Rev. Toxicol., 7:
1–35.
2. Howard, P. H. (1989) Handbook of environmental fate and exposure data for
organic chemical. Volume I. Large Production and Priority Pollutants; Lewis
Publishers: Chelsea, Michigan.
3. Xin-hua, X., Ping, H., Jian, J., and Zhi-wei, H. (2005) Fe salts as catalyst for the
wet oxidation of o-chlorophenol. J. Zhejiang Univ. Sci. B., 6: 569–570.
4. Mathialagan, T. and Viraraghavan, T. (2005) Biosorption of pentachlorophenol
by fungal biomass from aqueous solutions: A factorial design analysis. Environ.
Technol., 26: 571–580.
5. Kieth, L.H. and Telliard, W.A. (1979) Priority pollutants. Part I. A perspective
view. Environ. Sci. Technol., 13: 416–423.
6. Cui, C., Quan, X., Chen, S., and Zhao, H. (2005) Adsorption and electro
catalytic de-chlorination of pentachlorophenol on palladium-loaded activated
carbon fibers. Sep. Purif. Technol., 47: 73–79.
7. Lee, D.G. and Carlos, S.F. (1981) The oxidation of phenol and chlorophenols
by alkaline permanganate. Can. J. Chem., 59: 27–76.
8. Trapido, M., Hirvonen, A., Veressinina, Y., Hentunen, J., and Munter, R. (1997)
Ozonation, ozone/UV and UV/H2 O2 degradation of chlorophenols. Ozone Sci.
Eng., 19: 75–91.
9. Yuan, S.-H. and Lu, X.-H. (2005) Comparison treatment of various
chlorophenols by electro-Fenton method: relationship between chlorine con-
tent and degradation. J. Hazard. Mater.,118: 85–91.
10. Benitez, F.J., Beltran-Heredia, J., Acero, J.L., and Rubio, F.J. (2000) Contribution
of free radicals to chlorophenols decomposition by several advanced oxidation
processes. Chemosphere, 41: 1271–1277.
11. Prakash, P. and Franciscamary, L.J. (2005) Reaction of a sterically hindered iron
(III) porphyrin with peroxyacetic acid: degradation kinetics. J. Serb. Chem. Soc.,
70: 1105–1111.
12. Levitt, J.S, N’Guessan, A.L., Rapp, K.L., and Nyman, M.C. (2003) Remediation
of α-methylnaphthalene-contaminated sediments using peroxyacid. Water Res.,
37: 3016–3022.
13. Alderman, N.S., N’Guessan, A.L., and Nyman, M.C. (2007) Effective treat-
ment of PAH contaminated Superfund site soil with the peroxyacid process. J.
Hazard. Mater., 146: 652–660.
14. Sharma, S., Mukhopadhyay, M., and Murthy, Z.V.P. (2010) Degradation of 4-
chlorophenol in wastewater by organic oxidants. Ind. Eng. Chem. Res., 49:
3094–3098.
15. Estevinho, B.N., Martins, I., Nuno, R., Arminda, A., and Santos, L. (2007)
Removal of 2, 4-dichlorophenol and pentachlorophenol from waters by sorp-
tion using coal fly ash from a Portuguese thermal power plant. J. Hazard
Mater., 143: 535–540.
16. Radhika, M. and Palanivelu, K. (2006) Adsorptive removal of chlorophenols
from aqueous solution by low cost adsorbent-kinetics and isotherm analysis.
J. Hazard. Mater., 138: 116–124.
 Chlorophenol Remediation in Wastewater 289

17. Patel, U.D. and Suresh, S. (2006) Dechlorination of chlorophenols by

magnesium-palladium system. J. Coll. Interf. Sci., 299: 249–259.
18. Khodadoust, A.P., Wagner, J.A., Suidan, M.T., and Brenner, R.C. (1997)
Anaerobic treatment of PCP in fluidized-bed GAC bioreactors. Water Res., 31:
1776–1786.
19. Armenante, P.M., Kafkewitz, D., Lewandowski, G.A., and Jou, C.J. (1999)
Anaerobic-aerobic treatment of halogenated phenolic compounds. Water Res.,
33: 681–692.
20. Kim, M.H. and Hao, O.J. (1999) Cometabolic degradation of chlorophenols by
Acinatobacter species. Water Res., 33: 562–574.
21. Mikesell, M.D. and Boyd, S.A. (1986) Complete reductive dechlorination
and mineralization of pentachlorophenol by anaerobic microorganisms. Appl.
Environ. Microbiol., 52: 861–865.
22. Kao, C.M., Chai, C.T., Liu, J.K., Yeh, T.Y., Chen, K.F. and Chen, S.C. (2004)
Evaluation of natural and enhanced PCP biodegradation at a former pesticide
manufacturing plant. Water Res., 38: 663–672.
23. Esplugas, S., Yue, P., and Pervez, L. (1994) Degradation of 4-chlorophenol by
photolytic oxidation. Water Res., 28: 1323–1331.
24. Catalkaya, E.C. and Kargi, F. (2008) Advanced Oxidation of diuron by photo-
Fenton treatment as a function of operating parameters. J. Environ. Eng., 134:
1006–1013.
25. Pera-Titus, M., Garcia-Molina, V., Banos, M.A., Gimenez, J., and Esplugas,
S. (2004) Degradation of chlorophenols by means of advanced oxidation
processes: a general review. Appl. Catal. B., 47: 219–256.
26. Glaze, W.H., Beltran, F., Tuhkanen, T., and Kang, J.W. (1992) Chemical models
of processes. Water, Air, Soil Pollut., 27: 23–42.
27. Feuerstein, W. (1982) Untersuchung über die Anwendung von Fentons
Reagenz zur chemisch oxidativen Abwasserbehandlung (Investigations of
the application of Fenton’s reagent for chemical oxidation in wastewater
treatment), Dissertation, Kernforschungszentrum, Kahrlsuhe.
28. Weichgrebe, D. (1992) Chemisch oxidative Behandlung von
Deponiesickerwasser (Chemical oxidation treatment of deposit leachate),
Chem-.Ing-. Technol., 64: 438–440.
29. Legrini, O., Oliveros, E., and Braun. A. M. (1993) Photochemical processes for
water treatment. Chem. Rev., 93: 671–698.
30. Huang, C.P., Dong, C., and Tang, Z. (1993) Advanced chemical oxidation: Its
present role and potential future in hazardous waste treatment. Waste Manage.,
13: 361–377.
31. Andreozzi, R., Caprio, V., Insola, A., and Marotta R. (1999) Advanced oxidation
process (AOP) for water purification and recovery. Catal. Today, 53: 51–59.
32. Chiron, S., Fernandez-Alba, A., Rodriguez, A., and Garcia-Calvo, E. (2000)
Pesticide chemical oxidation: State of the art. Water Res., 34: 366–377.
33. Sun, H., Bai, Y., Liu, H., Jin, W., and Xu, N. (2009) Photocatalytic decom-
position of 4-chlorophenol over an efficient N-doped TiO2 under sunlight
irradiation. J. Photochem. Photobiol. A: Chem., 201: 15–22.
34. Venkatachalam, N., Palanichamy, M., and Murugesan, V. (2007) Sol-gel prepa-
ration and characterization of alkaline earth metal doped nano TiO2 : Efficient
photo catalytic degradation of 4-chlorophenol. J. Mol. Catal. A., 273: 177–185.
290 S. Sharma et al.

35. Lathasree, S., Rao, N.A., Siva Sankar, B., Sadasivam, V., and Rengaraj, K. (2004)
Heterogeneous photo catalytic mineralization of phenols in aqueous solutions.
J. Mol. Catal. A., 223: 101–105.
36. Wang, H. and Wang, J.L. (2008) The cooperative electrochemical oxidation
of chlorophenols in anode-cathode compartments. J. Hazard. Mater., 154:
44–50.
37. Manojlovic, D., Ostojic, D.R., Obradovic, B.M., Kuraica, M.M., Krsmanovic,
V.D., and Puric, J. (2007) Removal of phenol and chlorophenols from water
by new ozone generator. Desalination, 213: 116–122.
38. Poulopoulos, S.G., Nikolaki, M., Karampetsos, D., and Philippopoulos C.J.
(2008) Photochemical treatment of 2-chlorophenol aqueous solutions using
ultraviolet radiation, hydrogen peroxide and photo-Fenton reaction. J. Hazard.
Mater., 153: 582–587.
39. Chowdhury, P. and Viraraghavan, T. (2009) Sonochemical degradation of
chlorinated organic compounds, phenolic compounds and organic dyes-a
review. Sci. Total Environ., 407: 2474–2492.
40. Lin, J.G. and Ma, Y.S. (2000) Oxidation of 2-chlorophenol in water by
ultrasound/Fenton method. J. Environ. Eng., 126: 130–137.
41. Lin, C.H. and Tseng, S.K. (1999) Electrochemically reductive de-chlorination of
pentachlorophenol using a high over potential zinc cathode. Chemosphere, 39:
2375–2389.
42. Benitez, F.J., Beltran-Heredia, J., Acero, J. L., and Pinilla, M.L. (1997) Ozonation
kinetics of phenolic acids present in industrial wastewaters from olive oil mills.
Ind. Eng. Chem. Res., 36: 638–644.
43. Benitez, F.J., Beltran-Heredia, J., Gonzalez, T., and Real, F. (1995) Photo oxi-
dation of carbofuran by a polychromatic UV irradiation without and with
hydrogen peroxide. Photo oxidation of carbofuran by a polychromatic UV
irradiation without and with hydrogen peroxide. Ind. Eng. Chem. Res., 34:
4099–4105.
44. Glaze, W.H., Kang, J.W., and Chapin, D.H. (1987) The chemistry of water treat-
ment processes involving ozone, hydrogen peroxide and ultraviolet radiation.
Ozone Sci. Eng., 9: 335–352.
45. Hoigne, J. and Bader, H. (1983a) Rate constants of reactions of ozone with
organic and inorganic compounds in water-I. Water Res., 17: 173–183.
46. Hoigne, J. and Bader, H. (1983b) Rate constants of reactions of ozone with
organic and inorganic compounds in water-II. Water Res.17: 185–191.
47. Miller, R.M., Singer, G.M.; Rosen, J. D., and Bartha, R. (1988) Sequential degra-
dation of chlorophenols by photolytic and microbial treatment. Environ. Sci.
Technol., 22: 1215–1219.
48. Tezuka, M. and Iwasaki, M. (1998) Plasma induced degradation of
chlorophenols in aqueous solution. Thin. Sol. Films, 316: 123–127.
49. Willberg, D.M., Lang, P. S., Hochemer, R.H., Kratel, A., and Hoffmann,
M.R. (1996) Degradation of 4-chlorophenol, 3,4-dichloroaniline, and 2,4,6-
trinitrotoluene in an electro hydraulic discharge reactor. Environ. Sci. Technol.,
30: 2526–2534.
50. Lu, M.C. (1999) Oxidation of chlorophenols with hydrogen peroxide in the
presence of goethite. Chemosphere, 40: 125–130.
 Chlorophenol Remediation in Wastewater 291

51. Brillas, E., Mur, E., Sauleda, R., Sanchez, L., Peral, J., Domenech, X., and
Casado J. (1998) Aniline mineralization by AOPs: anodic oxidation, photo
catalysis, electro-Fenton and photo electro-Fenton processes. Appl. Catal., B.,
16: 31–42.
52. Tang, W.Z. and Huang C.P. (1995) The effect of chlorine positions of
chlorinated phenols of their dechlorination kinetics by Fenton’s reagent. Waste
Manage., 15: 615–622.
53. Tang, W.Z. and Huang, C.P. (1996) Effect of chlorine content of chlorinated
phenols on their oxidation kinetics by Fenton’s reagent. Chemosphere, 33:
1621–1635.
54. Li, Z., Kuo, C.H., and Zhongguo, Z. (2000) Advanced oxidation process of
chlorophenol- containing wastewater by ozone/hydrogen peroxide and its
kinetics. J. Environ. Eng., 19: 35–39
55. Cervera, S. and Esplugas, S. (1983) Obtencion de hidrogeno mediante fotolisis
del agua. Energia, 9: 103–107.
56. Hirvonen, A., Marina, T., Hentunen, J., and Tarhanen, J. 2000 Formation
of hydroxyleted and dimeric intermediates during oxidation of chlorinated
phenols in aqueous solution. Chemosphere, 41: 1211–1218.
57. Baum, G. and Oppenlaender, T. (1995) Vacuum-UV-oxidation of chloro-
organic compounds in an excimer flow through photo reactor. Chemosphere,
30: 1781–1790.
58. Oppenlander, T. and Gliese, S. (2000) Mineralization of organic micro pollu-
tants (homologous alcohols and phenols) in water by vacuum-UV-oxidation
(H2 O-VUV) with an incoherent xenon-excimer lamp at 172 nm. Chemosphere,
40: 15–21.
59. Benitez, F.J., Beltran-Heredia, J., Acero, J.L., and Rubio, F.J. (2000) Rate con-
stants for the reactions of ozone with chlorophenols in aqueous solutions. J.
Hazard. Mater., 79: 271–285.
60. Hong, P.K. and Zeng, Y. (2002) Degradation of pentachlorophenol by
ozonation and biodegradability of intermediates. Water Res., 36: 4243–4254.
61. Straehelin, S. and Hoigne, J. (1982) Mechanism and kinetics of decomposition
of ozone in water: rate of initiation by hydroxide ions and hydrogen peroxide.
Environ. Sci. Technol., 16: 676–681.
62. Kuo, W.S. (1999) Synergistic effects of combination of photolysis and
ozonation on destruction of chlorophenols in water. Chemosphere, 39:
1853–1860.
63. Hautaniemi, M., Kallas J., Munter, R., and Trapido, M. (1998) Modeling of
chlorophenol treatment in aqueous solutions. 1. Ozonation and ozonation
combined with UV radiation under acidic conditions. Ozone Sci. Eng., 20:
259–282.
64. Zeff, J. D. and Barich, J.T. (1990) Symposium on processes and treatment
of contaminated water and air: Wastewater technologies. Center, Ontario
(Canada).
65. Abe, K.I. and Tanaka, K. (1997) Fe3+ and UV-enhanced ozonation of
chlorophenolic compounds in aqueous medium. Chemosphere, 35: 2837–2847.
66. Benoit-Guyod, J.L., Bruckner, C., and Benoit-Guyod, M. (1994) Degradation of
chlorophenols by ozone and light. Fresen. Environ. Bull., 3: 331–338.
292 S. Sharma et al.

67. Mansilla, H.D., Gonzalez, E., Casas, S., Freer, J., Rodriguez, J., and Baeza,
J. (1995) The decomposition of chlorophenols by ozone/UV, in Proceedings
of the 12th Ozone World Congress, vol. 1, Lille, France, International Ozone
Association, European-African Group, Paris, France, 743–746.
68. Ruppert, G., Bauer, R., and Heisler, G. (1994) UV-O3 , UV-H2 O2 , UV-TiO2 and
the photo-Fenton reaction. Comparison of processes for wastewater treatment.
Chemosphere, 28: 1447–1454.
69. Shen, Y.S., Ku, Y., and Lee, K.C. (1996) Decomposition of chlorophenols in
aqueous solutions by UV/H2 O2 process. Toxicol. Environ. Chem., 54: 51–67.
70. Shen, Y.S., Ku, Y., and Lee, K.C. (1995) The effect of light absorbance on
the decomposition of chlorophenols by ultraviolet radiation and UV/H2 O2
processes. Water Res., 3: 907–914.
71. Benitez, F.J., Beltran-Heredia, J., Acero, J.L., and Rubio, F.J. (2001) Oxidation
of several chlorophenolic derivatives by UV irradiation and hydroxyl radicals.
J. Chem. Technol. Biotechnol., 76: 312–320.
72. Ku, Y., Leu, R.M., and Lee, K.C. (1996) Decomposition of 2-chlorophenol in
aqueous solution by UV irradiation with the presence of titanium dioxide.
Water Res., 30: 2569–2578.
73. Chamarro, E., Marco, A., and Esplugas, S. (2001) Use of Fenton reagent to
improve organic chemical biodegradability. Water Res., 35: 1047–1051.
74. Ormad, M.P., Ovelleiro, J.L., and Kiwi, J. (2001) Photo catalytic degrada-
tion of concentrated solutions of 2, 4-dichlorophenol using low energy light:
identification of intermediates. Appl. Catal., B., 32: 157–166.
75. Kwon, B.G., Lee, D.S., Kang, N., and Yoon, J. (1999) Characteristics of p-
chlorophenol oxidation by Fenton’s reagent. Water Res., 33: 2110–2118.
76. Walling, C. (1975) Fenton’s reagent revisited. Acc. Chem. Res., 8: 121–131.
77. Untea, I., Orbeci, C., and Tudorache, E. (2006) Oxidative degradation of 4-
chlorophenol from aqueous solution by photo-Fenton advanced oxidation
process. Environ. Eng. Manage. J., 5: 661–674.
78. Bokare, A.D. and Wonyong, C. (2010) Chromate-induced activation of hydro-
gen peroxide for oxidative degradation of aqueous organic pollutants.
Environ. Sci. Technol., 44: 7232–7237.
79. Bokare, A.D. and Wonyong, C. (2011) Advanced oxidation process based on
the Cr(III)/Cr(VI) redox cycle Environ. Sci. Technol., 45: 9332–9338.
80. Malato, S., Blanco, J., Fernandez-Ibanez, P., and Caceres, J. (2001) Treatment
of 2,4-dichlorophenol by solar photo catalysis: comparison of coupled photo
catalytic-active carbon vs. active carbon. J. Solar Eng., 123: 138–142.
81. Bard, A.J. (1980) Photo electrochemistry. Science, 207: 139–144.
82. Davis, A.P. and Huang, C.P. (1990) The removal of substituted phenols
by photo catalytic oxidation process with cadmium-sulfide. Water Res., 24:
543–550.
83. Gimenez, J., Curco, D., and Queral, M.A. (1999) Photo catalytic treatment of
phenol and 2,4-dichlorophenol in a solar plant in the way to scaling-up. Catal.
Today, 54, 229–243.
84. Hoffmann, M.R., Martin, S.T., Wonyong, C., and Bahnemann, D.W. (1995)
Environmental applications of semiconductors photo catalysis. Chem. Rev., 95:
69–96.
 Chlorophenol Remediation in Wastewater 293

85. Jones, A.P. and Watts, R.J. (1997) Dry phase dioxide-mediated photo catalysis:
basis for in situ surface destruction of hazardous chemicals. J. Environ. Eng.,
123: 974–981.
86. Rideh, L., Wehrer, A., Ronze, D., and Zoulalian, A. (1997) Photocatalytic degra-
dation of 2-chlorophenol in TiO2 aqueous suspension: modeling of reaction
rate. Ind. Eng. Chem. Res., 36: 4712–4718.
87. Jardim, W.F., Moraes, S.G., and Takiyama, M.M. K. (1997) Photo catalytic
degradation of aromatic chlorinated compounds using TiO2 : toxicity of
intermediates. Water Res., 31: 1728–1732.
88. Doong, R.A., Chen, C.H., Maithreepala, R.A., and Chang, S.M. (2001) The
influence of pH and cadmium sulfide on the photo catalytic degradation of
2-chlorophenol in titanium dioxide suspensions. Water Res., 35: 2873–2880.
89. Chen, Y.-C., Vorontsov, A.V., and Smirniotis, P.G. (2003) Enhanced photo
catalytic degradation of dimethyl methylphosphonate in the presence of
low-frequency ultrasound. Photochem. Photobiol. Sci., 2: 694–698.
90. Baraza, J. and Esplugas, S. (2000) Oxidacion avanzada en el tratamiento de
aguaresiduales. Tecnología del Agua, 197: 82–92.
91. Ku, Y. and Hsieh, C.B. (1992) Photo catalytic decomposition of 2, 4-
dichlorophenol in aqueous TiO2 suspensions. Water Res., 26: 1451–1456.
92. Linsebigler, A.L., Lu, G., and Yates Jr., J.T. (1995) Photo catalysis on TiO2
surfaces: principles, mechanisms and selected results. Chem. Rev., 95: 735–758.
93. Serpone, N., Maruthamuthy, P., Pichat, P., Pelizzetti, E., and Hidaka, H. (1995)
Exploiting the interparticle electron transfer process in the photo catalyzed oxi-
dation of phenol, 2-chlorophenol and pentachlorophenol: chemical evidence
for electron and hole transfer between coupled semiconductors. J. Photochem.
Photobiol. A., 85: 247–255.
94. Satuf, M. L., Jose, S., Paggi, J.C., Brandi, R. J., Cassano, A.E., and Alfano,
O.M. (2010) Reactor modeling in heterogeneous photocatalysis: toxicity and
biodegradability assessment. Water Sci. Technol., 61: 2491–2499.
95. Czaplicka, M. (2006) Photo-degradation of chlorophenols in the aqueous
solution. J. Hazard. Mater.,134: 45–59.
96. Androulaki, E., Hiskia, A., Dimotikali, D., Minero, C., Calza, P., Pelizzetti,
E., and Papaconstantinou, E. (2000) Light induced elimination of mono and
polychlorinated phenols from aqueous solutions by PW12O40 3-The case of
2,4,6-trichlorophenol. Environ. Sci. Technol., 34: 2024–2028.
97. Bandara, J., Mielczarski, J.A., Lopez, A., and Kiwi, J. (2001) Sensitized degra-
dation of chlorophenols on iron oxides induced by visible light. Comparison
with titanium oxide. Appl. Catal., B., 34: 321–333.
98. Herrmann, J.M., Guillard, Ch., Disdier, J., Lehaut, C., Malato, S., and Blanco,
J. (2002) New industrial titania photo catalysts for the solar detoxification of
water containing various pollutants. Appl. Catal., B., 35: 281–294.
99. Yoon, J., Kim, S., Lee, D.S., and Huh, J. (2000) Characteristics of
p-chlorophenol degradation by photo-Fenton oxidation. Water Sci. Technol.,
42: 219–224.
100. Shulpin, G.B., Bochkova, M.M., Nizova, G.V., and Kozlova, N.B. (1997)
Aerobic photo degradation of phenols in aqueous solutions promoted by metal
compounds. Appl. Catal., B., 12: 1–19.
294 S. Sharma et al.

101. Munter, R., Preis, S., Kamenev, S., and Siirde, E. (1993) Methodology of
ozone introduction into water and wastewater treatment. Ozone Sci. Eng., 15:
149–165.
102. Vollmuth, S. and Niesser, R. (1995) Degradation of PCDD, PCDF, PAH, PCB
and chlorinated phenols during the destruction-treatment of landfill seepage
water in laboratory model reactor (UV, ozone, and UV/ozone). Chemosphere,
30: 2317–2331.
103. Huling, S.C.G., Arnold, R.G., Sierka, R.A., Jones, P.K., and Fine, D.D.
(2000) Contaminant adsorption and oxidation via Fenton reaction. J. Environ.
Eng.,126: 595–600.
104. Sabhi, S. and Kiwi, J. (2001) Degradation of 2,4-dichlorophenol by immobi-
lized iron catalysts. Water Res. 35: 1994–2002.
105. Herrmann, J.M., Matos, J., Disdier, J., Guillard, Ch., Laine, J.., Malato, S., and
Blanco, J. (1999) Solar photo catalytic degradation of 4-chlorophenol using the
synergistic effect between titania and activated carbon in aqueous suspension.
Catal. Today, 54: 255–265.
106. Bauer, R., Waldner, G., Fallmann, H., Hager, S., Klare, M., Krutzler, T., Malato,
S., and Maletzky, P. (1999) The photo-Fenton reaction and the TiO2 /UV
process for wastewater treatment-novel developments. Catal. Today, 53:
131–144.
107. Yue, B., Zhou, Y., Xu, J., Wu, Z., Zhang, X., Zou, Y., and Jin, S. (2002)
Photo catalytic degradation of aqueous 4-chlorophenol by silica-immobilized
polyoxometalates. Environ. Sci. Technol., 36: 1325–1329.
108. Davis, R.A., Rinker, R.G.J., and Sandall, O.C. (1995) Kinetics of the reaction of
ozone with 2,4,6-trichlorophenol. J. Hazard. Mater., 41: 65–72.
109. Ghaly, M.Y., Hartel, G., Mayer, R., and Haseneder, R. (2001) Photochemical
oxidation of p-chlorophenol by UV/H2 O2 and photo-Fenton process: A
comparative study. Waste Manage., 21: 41–47.
110. Jimenez, A.E., Estrada, C.A., Cota, A.D., and Roman, A. (2000) Photo catalytic
degradation of DBSNa using solar energy. Sol. Energy Mater. Sol. Cells, 60:
85–95.
111. Kaczmarek, H., Drag, R., Swiatek, M., and Oldak, D. (2002) The influence of
UV-irradiation on poly (vinyl chloride) modified by poly (vinyl acetate). Surf.
Sci., 507: 877–882.
112. Chan, Y.Ch., Chen, J.N., and Lu, M.Ch. (2001) Intermediate inhibition in the
heterogeneous UV-catalysis using a TiO2 suspension system. Chemosphere, 45:
29–35.
113. Oussi, D., Mokrini, A., and Esplugas, S. (1997) Removal of aromatic com-
pounds using UV/H2 O2 . Photochem. Photobiol., 1: 77–83.
114. Heinzle, E., Stockinger, H., Stern, M., Fahmy, M., and Kut, O.M. (1995)
Combined biological-chemical (ozone) treatment of wastewaters containing
chloroguaiacols. J. Chem. Technol. Biotechnol., 62: 241–252.
115. Ledakowicz, S. (1998) Integrated processes of chemical and biological oxida-
tion of wastewaters. Environ. Protect. Eng., 24: 35–47.
116. Pitter, P. and Chudoba, J. (1991) Biodegradability of Organic Substances in the
Aqueous Environment, CRC Press: Boca Raton, FL.
 Chlorophenol Remediation in Wastewater 295

117. Al Momani, F., Ben Abderrazik, N., Sans, C., and Esplugas, S. (2001) Impact
of advance oxidation technology on biological treatment. Effect on COD and
biodegradability. The 7th AOT´s: Niagara Falls, Canada.
118. Scott, J.P. and Ollis, D.F. (1996) Engineering model of combined chemical and
biological processes. J. Environ. Eng., 122: 1110–1114.
119. Scott, J.P. and Ollis, D.F. (1995) Integration of chemical and biological oxida-
tion processes for water treatment: Review and recommendations. Environ.
Prog., 14: 88–103.
120. Sarria, V., Deront, M., Peringer, P., and Pulgarin, C. (2003) Degradation of
a biorecalcitrant dye precursor present in industrial wastewaters by a new
integrated iron (III) photo assisted-biological treatment. Appl. Catal., B., 40:
231–246.
121. Contreras, S., Rodriguez, M., Al Momani, F., Sans, C., and Esplugas, S. (2003)
Contribution of the ozonation pre-treatment to the biodegradation of aqueous
solutions of 2, 4-dichlorophenol. Water Res., 37: 3164–3171.
122. Bacardit, J., Garcia-Molina, V., Bayarri, B., Gimenez, J., Chamarro, E., Sans,
C., and Esplugas, S. (2007) Coupled photochemical-biological system to treat
biorecalcitrant wastewater Water Sci. Technol., 55(12), 95–100.
123. Vogelpohl, A., Sievers, M., and Geilssen, S.U., Eds. (2007) Oxidation
Technologies for Water and Wastewater Treatment IV . International Water
Association (IWA) Publication: London, UK.
124. Rosenfeldt, E. and Linden, K.G. (2004) Degradation of endocrine disrupting
chemicals bisphenol A, ethinylestradiol, and estradiol during UV photolysis
and advanced Oxidation processes. Environ. Sci. Technol., 38: 5476–5483.
125. Jiang, J.Q., Yin, Q., Zhou, J. L., and Pearce, P. (2005) Occurrence and treatment
trials of endocrine disrupting chemicals (EDCs) in wastewaters. Chemosphere,
61: 544–550.