ARTICLE IN PRESS

Water Research 38 (2004) 42134221

www.elsevier.com/locate/watres

A study of the reaction mechanisms of the degradation of

2,4-dichlorophenoxyacetic acid by oxalate-mediated
photooxidation
C.Y. Kwan, W. Chu
Department of Civil and Structural Engineering, Research Centre for Environmental Technology and Management,
The Hong Kong Polytechnic University, Hunghom, Kowloon, Hong Kong
Received 28 January 2004; received in revised form 23 April 2004; accepted 23 June 2004

Abstract

The oxidation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by FeII/H2O2/UV (FHU) and ferrous-oxalate/
H2O2/UV (FOHU) processes was investigated and compared. The initial decay rate and the overall removal percentage
were used as the performance indexes. To extensively explore the associated processes, the intermediates and the end
products were also examined and compared. The results showed that the degradation of 2,4-D by FHU is slower than
that of FOHU. The involvement of ferrous-oxalate in the reaction can greatly improve the initial decay rate of 2,4-D
because of the higher light sensitivity of the organometallic complexes. The total removal of 2,4-D and its
corresponding intermediates was found to be strongly dependent on the initial hydrogen peroxide concentration; an
excessively low initial [H2O2] will terminate the process due to the deciency of hydroxyl radicals in the solution. All of
the major primary intermediates (2,4-dichlorophenol, 2-chloro-4-hydroxyphenoxyacetic acid, 4-chloro-2-hydroxyphe-
noxyacetic acid, 5-hydroxy-2,4-dichlorophenoxyacetic acid and 6-hydroxy-2,4-dichlorophenoxyacetic acid) have been
identied and conrmed by LC-MS. A reaction mechanism was proposed for FHU and FOHU and veried by the
evidence presented in this study.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: 2,4-dichlorophenoxyacetic acid; Ferrous ion; Ferrous oxalate; Hydrogen peroxide; Oxidation; UV

1. Introduction and is used in many commercial products (Munro et al.,

The herbicide 2,4-Dichlorophenoxyacetic acid (2,4-
D), rst registered for use in the United States in 1948,
has been the most commonly and widely used acidic
phenoxy herbicide throughout the world for more than
fty years. It is often formulated as amine salts or low
volatile esters through various manufacturing processes,
Corresponding author. Tel.: +852-2766-6075; fax: +852-
2334-6389.
E-mail address: cewchu@polyu.edu.hk (W. Chu).
1992). 2,4-D is primarily used in agriculture, forestry,
and lawn care practices. Over 60% of the total usage of
2,4-D in the US is for weed control in corn and small-
grain elds (EPA, 1997). Additional uses of 2,4-D are in
recreational areas, parks, golf courses, roadsides,
industrial sites, aquatic situations, and gardening. Plants
absorb 2,4-D through their roots and leaves within four
to six hours after application (EPA, 1989). The residue
may then leach below the root zone and rapidly
contaminate the moving water or groundwater, as the
herbicide is highly water-soluble (i.e., 900 mg/L at

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2004.06.033
 ARTICLE IN PRESS
4214 C.Y. Kwan, W. Chu / Water Research 38 (2004) 42134221
25 1C). de Amarante et al. (2003) have suggested that
2,4-D is detectable in surface water and ground water
not only during the application of the herbicide, but also
after a long period of use. For example, 2,4-D and its
major transformation product, 2,4-dichlorophenol (2,4-
DCP), were detectable in 15 days after the application of
2,4-D to eucalyptus crops. As 2,4-D is released to water,
the degradation rates of 2,4-D by microorganisms
depend on the level of nutrients present, the tempera-
ture, availability of oxygen, and degree of contamina-
tion by 2,4-D and other phenoxyacetic acids. It was
reported that the half-life of 2,4-D in aquatic environ-
ments ranges from one week to several weeks under
oxygenated conditions (Howard, 1991).
Advanced oxidation processes (AOPs) are effective
remediation methods using high oxidation-potential
sources to produce the primary oxidant species, the
hydroxyl radical (HOd), which reacts rapidly and
unselectively with most organic compounds. Due to
the non-specic and high electron afnity of the
hydroxyl radical, the degradation products can be
hydroxylated or partially oxidized intermediates, dimer-
ized compounds, carbon dioxide, and mineral acids
(Klare et al., 2000). It has been shown that 2,4-D can be
successfully degraded by various AOPs, including
Fentons reaction (Pignatello, 1992), Photo-Fenton
(Sun and Pignatello, 1993), UV/H2O2 process (Chu,
2000; Alfano et al., 2001), UV/TiO2 (Trillas et al., 1995,
1996), Anodic Fenton (Brillas et al., 1998, 2000),
Ozonation (Chiron et al., 2000; Hu et al., 2000), and
Catalyzed Ozonation (Piera et al., 2000; Brillas et al.,
2003). Apart from the above radical-mediated oxida-
tions, high-frequency sonolysis can also degrade 2,4-D,
which generates intermediates such as 2,4-DCP, 4-
chlorocatechol, and chlorohydroquinone (CHQ) (Peller
et al., 2001).
The use of ferrous oxalate instead of ferrous ions in
the UV/H2O2 system to accelerate the production of
hydroxyl radicals is a new approach. Detailed informa-
tion regarding the reaction mechanism of this oxalate-
mediated photooxidation process is very limited. In this
study, the photodegradation performances of 2,4-D by
FeII/UV/H2O2 and ferrous-oxalate/UV/H2O2 at two
different initial H2O2 levels were compared by examin-
ing their intermediates.
2. Methodologies
2.1. Materials
The chemicals 2,4-D, 2,4-DCP, CHQ, iron(II) sulfate-
7-hydrate (FeSO4
7H2O) were purchased from Riedel-
de Haen, while 4,6-dichlororesorinol was obtained from
Tokyo Chemical Industries. 4-chlorocatechol and 3,5-
dichlorocatechol were from Aldrich. 2-chloro-1,4-ben-
zoquinone was from Acros. All stock solutions were
prepared in deionized distilled water, where 2,4-D and
2,4-DCP were prepared at 2.26 mM and 0.61 mM,
respectively. Ferrous sulfate was freshly made in
diluted sulfuric acid. A high-performance liquid
chromatography (HPLC) grade acetonitrile,
methanol, HPLC-water and acetic acid were bought
from LAB-SCAN, 30% Hydrogen peroxide and
potassium oxalate (K2C2O4
H2O) were obtained f
rom British Drug Houses (BDH). All of the chemicals
were used as received, without undergoing further
purication.
2.2. Method
For each photolysis experiment, stock solutions of
potassium oxalate and Fe(II) sulfate were mixed and
stirred for at least 45 min in the beaker covered with
aluminum foil to minimize the unnecessary exposure of
the mixture to the light. The pH level of the reaction
solution was adjusted by either 6 M of sodium hydroxide
or 3 M of sulfuric acid to a predetermined level of 2.8.
Then, 2,4-D was added to the premixed solution,
allowing another 15 min of stirring to ensure homo-
geneity. The well-stirred solution was transferred to a
400 mL quartz cylinder placed inside an RPR-200
RayonetTM photochemical reactor with an installed
cooling fan. The reactions were initiated by adding
diluted hydrogen peroxide and simultaneously turning
on the pre-warmed UV lamps. The solution was exposed
to four 253.7 nm phosphor-coated low-pressure
mercury lamps with a total photon intensity of
6.0  106 Einstein/s/L at room temperature around
20 1C. The initial concentration of the probe compound
at time zero was determined from an unexposed sample.
Exactly, 1 mL of the illuminated sample was taken out
from the photoreactor at pre-determined time intervals
and mixed with 1 mL of methanol to quench the process.
The parent compound and intermediates were then
quantied by LC analysis with a ThermoQuest
Hyperails ODS column, in which a linear mobile-phase
gradient was programmed from 100% of 0.15%
acetic acid to 50% of acetic acid (0.15%) and 50%
acetonitrile in 25 min and then held for 5 min at a ow
rate of 1.0 mL/min for the separation of 2,4-D, 2,4-DCP
and all the intermediates. A Finnigan LCQTM DUO ion
trap mass spectrometer coupled to the LC was used to
verify the reaction intermediates through electrospray
ionization (ESI) associated with a negative operational
mode. Some of the intermediates were not purchasable
from the supplier, the quantications of 2-Cl-4-OH-
PAA, 4-Cl-2-OH-PPA, 5-OH-2,4-D, and 6-OH-2,4-D
were calculated from the UV absorptivity of
2,4-D, because of their similar molecular structures
(Zona et al., 2002).
 ARTICLE IN PRESS
C.Y. Kwan, W. Chu / Water Research 38 (2004) 42134221 4215

3. Results and discussion 1

3.1. Reaction kinetics 0.9

Mass balance
2,4-D
The photooxidation of 2,4-D was investigated under 0.8
Total intermediate
various conditions and the results of 2,4-D decay and 2,4-DCP
0.7 Intermediate A & B
the curves of the generation/degradation of its inter-

Concentration (mM)
Intermediate C & D
mediates throughout the reactions of FeII/H2O2/UV
0.6
(FHU) and ferrous-oxalate/H2O2/UV (FOHU) were
summarized in Figs. 14, in which the solutions contain 0.5
0.1 mM of Fe2+ and 1 or 3 mM H2O2 in the presence or
absence of 1.2 mM oxalate. 0.4
At a lower dosage of [H2O2] (1 mM), it is interesting
to note that a two-stage degradation of 2,4-D was 0.3
observed as shown in Figs. 1 and 2. During this these
two stages, 2,4-D was decayed exponentially with a fast 0.2
initial rate, followed by a retarded decay rate in the
second stage. This is because the advanced oxidation 0.1
was dominated by the aggressive radical (HOd) in the
solution; its concentration is higher at the beginning of 0
0 300 600 900 1200 1500 1800
the reactions due to the unrestricted supply of H2O2, Time (s)
(through its reactions involving Fe2+, ferrous-oxalate
and UV). However, the transformation of 2,4-D would Fig. 2. The decay of 2,4-D and the formation of intermediates
gradually slow down, as the hydrogen peroxide was in the FOHU (low [H2O2]) process at 253.7 nm containing
0.1 mM of Fe2+, 1.2 mM of oxalate, and 1 mM of H2O2 at a pH
depleting during the oxidative reaction because of the
of 2.8. The total intermediate curve is the sum of all measurable
intermediates.
1
Mass balance
0.9 2,4-D consumption of Fe2+/ferrous-oxalate (Eqs. (1) and (2))
Total intermediate (Kwan and Chu, 2003) or photolysis to hydroxyl
2,4-DCP
0.8 Intermediate A & B
radicals (Eq. (3)) (Chu, 2000). Nogueira and Guimaraes
Intermediate C & D (2000) reported the concentration of hydrogen peroxide
0.7 dropped below the detection limit during the irradiation
of dichloroacetic acid by ferrioxalate/H2O2 system. As
Concentration (mM)

0.6 the [H2O2] dropped to a lower level in the solution, the

oxidation through hydroxyl radicals became minor,
0.5 while the direct photolysis became the sole but less
effective mechanism available for the decay of 2,4-D. In
0.4 addition, the formation of intermediates in the solution
induce additional sub-reactions that compete for the
0.3 remaining hydroxyl radicals with the parent compound,
thus the degradation of 2,4-D is reduced signicantly at
0.2
the second stage.
0.1 Fe2 H2 O2 hn ! Fe3 HOd OH ; (1)

0
0 300 600 900 1200 1500 1800 2100 2400 2700 FeII C2 O4 H2 O2 hn ! FeIII C2 O4 HOd OH ;
Time (s) (2)
Fig. 1. The decay of 2,4-D and the formation of intermediates
in the FHU (low [H2O2]) process at 253.7 nm containing H2 O2 hn ! 2HOd : (3)
0.1 mM of Fe2+ and 1 mM of H2O2 at a pH of 2.8. The total
intermediate curve is the sum of all measurable intermediates. By comparing Figs. 1 and 2, the nal fractions of
The mass balance of the benzene ring curve is the combination 2,4-D removal are about the same for the two low
of 2,4-D and all of the ringed-products. Intermediates A, B, C, [H2O2] cases, while the FOHU system achieved this level
and D represent 5-OH-2,4-D, 6-OH-2,4-D, 2-Cl-4-OH-PAA, 20 min earlier than that without oxalate (FHU). The
and 4-Cl-2-OH-PAA, respectively. initial decay rate of 2,4-D in the former was determined
 ARTICLE IN PRESS
4216 C.Y. Kwan, W. Chu / Water Research 38 (2004) 42134221

to be 0.0022 s1, which is 2.75 times higher than that of 1

the latter; this is likely because the ferrous-oxalate
complexes (including FeIIC2O4 and/or FeII(C2O4)2 2
0.9
depending on the solutions pH (Park et al., 1997)) are
0.8 Mass balance
highly photosensitive compounds and react much more
2,4-D
quickly and effectively with H2O2 and UV than with Total intermediate
uncomplexed Fe2+ in generating hydroxyl radicals. 0.7
2,4-DCP

Concentration (mM)
Likewise, the use of a higher initial [H2O2] at 3 mM in Intermediate A & B
0.6
the FOHU process also speeds up the 2,4-D transforma- Intermediate C & D
tion by 1.9 times that of FHU. However, the overall
0.5
removal of 2,4-D increased from 72% to 99.9% as
[H2O2] increased from 1 to 3 mM for both FHU and
0.4
FOHU, as illustrated in Figs. 3 and 4.
As illustrated in Fig. 5, the pseudo-rst order decay
0.3
rates between the high/low [H2O2] for both the FHU
and FOHU systems, where the 2,4-D decay rate is 0.2
enhanced due to the increment of [H2O2] (from 1 to
3 mM), are quite signicant (1.3 and 1.9 times in the 0.1
FHU and FOHU, respectively). It is interesting to note
that the level of [H2O2] has a signicant effect in 0
determining the pattern of 2,4-D decay. When the initial 0 300 600 900 1200 1500 1800
[H2O2] level is low, the process will abruptly cease and Time (s)
this results in a two-stage pattern. However, such a Fig. 4. The decay of 2,4-D and the formation of intermediates
termination of process can be prevented if a higher in a FOHU (high [H2O2]) process at 253.7 nm, containing
[H2O2] is used. This is because the radical attack is the 0.1 mM of Fe2+, 1.2 mM of oxalate, and 3 mM of H2O2 at a pH
major reaction mechanism for degrading 2,4-D, where of 2.8.
sufcient H2O2 is crucial to ensuring the adequate
production of hydroxyl radicals in the solution. 0
Although there is no signicant two-stage pattern for
high [H2O2] cases, it was noted that the 2,4-D decay rate
-1

0.9 -2
Mass balance
0.8 2,4-D
ln C/Co

Total intemediate -3
0.7 2,4-DCP
Concentration (mM)

Intermediate A & B
0.6 Intermediate C & D
-4
FHU/1mM H2O2
0.5
FHU/3mM H2O2
0.4 -5 FOHU/1 mM H2O2
FOHU/3 mM H2O2
0.3

-6
0.2 0 500 1000 1500 2000 2500
Time (s)
0.1
Fig. 5. The pseudo rst-order decay of 2,4-D in both FHU and
0 FOHU processes at low (1 mM) and high (3 mM) initial [H2O2]
0 300 600 900 1200 1500 1800 levels.
Time (s)

Fig. 3. The decay of 2,4-D and the formation of intermediates in FHU was progressively accelerated over the whole
in a FHU (high [H2O2]) process at 253.7 nm, containing 0.1 mM process. This is likely due to the Fe3+ sensitization
of Fe2+ and 3 mM of H2O2 at a pH of 2.8. effect. The Fe3+ ion is known to be a by-product during
 ARTICLE IN PRESS
C.Y. Kwan, W. Chu / Water Research 38 (2004) 42134221 4217

the generation of hydroxyl radicals (Eq. (1)), and Fe3+
is capable of undergoing spontaneous-hydrolysis with
water to form FeOH2+, Fe(OH)+ 4+
2 , Fe2(OH)2 , and
0
Fe(OH)3 in the absence of other chelating ligands
(Martin et al., 1998). Pignatello et al. (1992) stated that
monohydroxy complex (FeOH2+) is the predominant
species in the pH level of our case (2.8) and is able to
produce hydroxyl radicals directly through the photo-
sensitization reaction (Eq. (4)), while simultaneously
regenerating Fe2+ to induce more hydroxyl radicals
through Eq. (1),
FeOH2 hn ! Fe2 HOd : (4)
Since Fe3+ and FeOH2+ are absent in the solution at
the very beginning, and it takes some time to form and
accumulate high enough levels of [Fe3+] and [FeOH2+]
for the photo-sensitization reaction, the self-catalytic is
therefore observed. On the other hand, the ferrous-
oxalate complexes cannot be further hydrolyzed like
Fe3+, so such a mechanism is not observed in the
FOHU as justied in Fig. 5.
Fig. 6 shows the transformation of 2,4-D by FHU and
FOUH at two extreme conditions (i.e., low [Fe2+] with
high [H2O2] and high [Fe2+] with low [H2O2]). As [Fe2+]
remained at 0.1 mM and [H2O2] increased to 5 mM, the
degradation rate of 2,4-D accelerated and the curves
shifted further to the left but enhancement due to the
addition of 1.2 mM oxalate became less obvious than the
previous two cases with [H2O2]=1 and 3 mM. For the
1 degradation of primary and secondary intermediates), as
0.9 FOHU_A
FHU_A
0.8 FHU_B
FOUH_B
0.7
0.6
C/Co
experiments conducted at [Fe2+]=1 mM and
[H2O2]=0.5 mM, the C/Co curves exhibited a sharp
drop (i.e., almost 50% of 2,4-D was removed in 150 s)
and then leveled off. The rapid initial decay can be
explained by the vigorous reactions between H2O2 with
excess ferrous ions or ferrous oxalate, as a result, low
amount of hydrogen peroxide was used up in a very
short period of time in rst stage. It is wroth noting that
the second stage of FHU is slightly faster than that of
the FOHU because large quantities of Fe2+ were
oxidized to uncomplexed Fe3+ in the absence of oxalate.
As mentioned before, high levels of [Fe3+] and
[FeOH2+] initiate the photo-sensitization reaction (Eq.
(4)) which provides hydroxyl radicals without the use of
hydrogen peroxide.
3.2. Oxidation products
Figs. 1 and 2 (the low [H2O2] cases) also indicated the
mass balance of benzene rings that followed the trend of
the 2,4-D decay, but at a slower rate. At the end of the
reactions, about 40% and 50% of the rings were opened
(or even mineralized) in the FHU and FOHU,
respectively, while the remaining ring mass was equally
contributed by the residual 2,4-D and its derivatives in
the solution. Furthermore, the total intermediate mass
increased at the commencement of the process but
leveled off afterwards due to the deciency of H2O2.
This can be justied by comparing the trend of
intermediate curves at the high [H2O2] levels, where
the curves increased initially and then declined (i.e., the
shown in Figs. 3 and 4. Moreover, the interception of
the mass curve and the total intermediate curve in Figs.
3 and 4 implied that 2,4-D was completely transformed
in 30 min and that the remaining aromatics in the
solution came solely from the intact intermediates. That
the mass curves declined to 10% at the end of the
process suggested that 90% of the end products are non-
aromatic compounds such as simple organic acids and

0.5 that the remaining 10% of aromatic intermediates

should be degradable at an extended reaction time if
0.4 additional [H2O2] could be added to the systems.
All the measurable intermediates were also identied
0.3
in this study, including 2,4-DCP, 2-chloro-4-hydroxy-
phenoxyacetic acid (2-Cl-4-OH-PAA), 4-chloro-2-hy-
0.2
droxyphenoxyacetic acid (4-Cl-2-OH-PPA), 5-hydroxy-
0.1 2,4-dichlorophenoxyacetic acid (5-OH-2,4-D), and 6-
hydroxy-2,4-dichlorophenoxyacetic acid (6-OH-2,4-D),
0 where the 2,4-DCP was found to be the dominant
0 300 600 900 1200 1500 1800 species among them (see Figs. 14). The mass spectra of
Time (s) all identied intermediates were summarized in Table 1.
Fig. 6. The transformation of 1.0 mM 2,4-D by FHU and The [2,4-DCP] increased rapidly at the initiation of 2,4-
FOHU at two extreme conditions: (A) [Fe2+]=1.0 mM and D degradation. The 2,4-DCP then started to accumulate
[H2O2]=0.5 mM, and (B) [Fe2+]=0.1 mM and [H2O2]=5 mM. in the solution or to further decay to secondary
The initial pH was 2.8. intermediates depending on the availability of [H2O2]
 ARTICLE IN PRESS
4218 C.Y. Kwan, W. Chu / Water Research 38 (2004) 42134221

Table 1
Summary of the intermediates identied by LC/MS in this study

Intermediates Characteristic m/z ions Remarks

  
Hydroxy-2,4-dichlorophenoxyacetic acid (OH-2,4-D) 235 [M-H] , 237 [M+2-H] , 239 [M+4-H] Major intermediates A and B
Chlorotrihydroxyphenoxyacetic acid 233 [M-H], 235 [M+2-H] At low level
Chlorodihydroxyphenoxyacetic acid 217 [M-H], 219 [M+2-H] At low level
Chlorohydroxyphenoxyacetic acid (Cl-OH-PAA) 200.6 [M-H], 202.6 [M+2-H] Major intermediates C and D
Dichlorohydroxybenzoquinone 191 [M-H], 193 [M+2-H], 195 [M+4-H] At low level
3,5-dichlorocatechol 177 [M-H], 179 [M+2-H], 181 [M+4-H] At low level
4,6-dichlororesorinol
2,4-dichlorophenol 161 [M-H], 163 [M+2-H], 165 [M+4-H] Major intermediate 2,4-DCP
Chlorohydroquinone (CHQ) 143 [M-H], 145 [M+2-H] At low level
4-chlorocatechol
2-chloro-1,4-benzoquinone 141 [M-H], 143 [M+2-H] At low level

in the solution, where the principle of the higher the
initial [H2O2] the higher the decay rates was analogous
to that of 2,4-D decay. The formation and decay of
other intermediates also followed similar trends but in
lower concentrations, while the total yields of 5-OH-2,4-
D and 6-OH-2,4-D were slightly greater than that of the
isomers of 2-Cl-4-OH-PAA and 4-Cl-2-OH-PPA.
3.3. Reaction mechanism
A study of the evolution proles of these intermedi-
ates offered useful information for exploring the
mechanism, and the degradation pathways were pro-
posed accordingly to illustrate a series of degradation
steps in the transformation of 2,4-D, as shown in
Fig. 7. The major decay pathway of 2,4-D upon
hydroxyl radical attack is through the homolysis of its
C1O bond on the aromatic ring to give 2,4-DCP and
glycolic acid (Zona et al., 2002; Brillas et al., 2003). This
should be the predominant step, because the primary
approach to synthesizing 2,4-D is the condensation
of 2,4-dichlorophenol with monochloroacetic acid
(WHO, 1984).
To verify the secondary and tertiary oxidation
products from 2,4-DCP, elevated [2,4-DCP] (around
1 mM) was photolyzed in a solution containing 0.1 mM
Fe2+, 1.2 mM oxalate, and 3 mM H2O2 at pH 2.8. The
hydroxyl radical may replace the chlorine atom of 2,4-
DCP at either the para-position to form chlorohydro-
quinone (CHQ) or the ortho-position to yield 4-
chlorocatechol, yet many studies suggested that HOd
radicals should predominantly attack chlorophenols at
the para site (Bandara et al., 2001; Ma et al., 2001). This
is because the OH group in the phenolic ring is ortho-
and para-directing with activation, which means the
electrophilic hydroxyl radical will attack the electron-
rich positions at the ortho- and para-sites. However, the
HOd adduct at the para-position may experience less
steric strain than that at the ortho-position, and the
inductive electron-withdrawing effect of the chlorine
atom might render attachment of the electrophilic
hydroxyl radical to the ortho- relative to the para-
position. These are the reasons why para-substitution
overrides ortho-substitution, resulting in a faster oxida-
tion of 2,4-DCP to CHQ. Subsequently, CHQ may
dissociate two hydrogen atoms to give 2-chloro-1,4-
benzoquinone upon further hydroxyl radical attacks. As
such, high yields of CHQ and its corresponding quinone
were observed, indicating that the para-site was the most
preferential for HOd radical attacks on Chlorophenols.
A similar observation was also reported in the photo-
degradation of 2,4-D in titanium dioxide suspensions
(DOliveira et al., 1993).
On the other hand, 2,4-DCP may also be transformed
through hydroxylation or electrophilic aromatic sub-
stitution. This allows an electrophile, the OH group, to
be introduced onto the aromatic ring. Thus, 2,4-DCP
can be hydroxylated by HOd, leading to isomers of 3,5-
dichlorocatechol and 4,6-dichlororesorcinol (as indi-
cated by two peaks exhibiting a 9:6:1 cluster at m=z
177 [M-H], 179 [M+2-H], and 181 [M+4-H] in the
chromatograph under negative ionization). Likewise,
Brillas et al. (2000) also reported the 4,6-dichlororesorc-
inal as the product of 2,4-DCP hydroxylation. The two
isomers would then undergo further hydroxylation, but
such intermediates were not detectable because they
were rapidly dehydrogenated to their corresponding
quinone (as detected at m=z 191 [M-H], 193 [M+2-
H], and 195 [M+4-H] with a splitting ratio of 9:6:1,
characterized by two typical 35Cl/37Cl atom clusters).
Judging from the MS information, the most likely
compound is 3,5-dichloro-2-hydroxy-1,4-benzoquinone,
which was also suggested by Lopez et al. (2003). Finally,
the further oxidation of this chlorobenzoquinone and
other hydroxylated products will break the aromatic
rings, giving maleic and fumaric acids. These acids can
 ARTICLE IN PRESS
C.Y. Kwan, W. Chu / Water Research 38 (2004) 42134221 4219

Fig. 7. The proposed reaction pathway for the transformation of 2,4-D.

compete for HOd radicals, resulting in simpler organic which will eventually and gradually be mineralized to
acids (via decarboxylation) such as acetic acid, formic carbon dioxide (Brillas et al., 2000; Comninellis and
acid, glyoxylic acid, and oxalic acid (Zona et al., 2002), Nerini, 1995).
 ARTICLE IN PRESS
4220 C.Y. Kwan, W. Chu / Water Research 38 (2004) 42134221
Nevertheless, a side reaction involving dimerization
may occur because the mass spectrum of the reaction
shows a characteristic multiplet pattern of a molecular
ion containing three chlorine atoms at m/z 303, 305,
307, and 309 under negative ionization. Since the
formation of dimeric products in diluted aqueous
solutions is possible as a result of the recombination of
chlorophenol free radicals (Skurlatov et al., 1997); this
trichlorinated dimer should be derived from the
combination of 2,4-DCP and CHQ radicals, which was
also reported in the 2,4-DCP degradation by UV/H2O2
or ozonation and suggested to be trichloro-trihydroxy
biphenyl (Hirvonen et al., 2000). However, the forma-
tion of dimer will not cause signicant environmental
problems since only a trace amount of dimeric product
was detected, and it was fully degradable by the FHU
and FOHU processes. Given that the trace trichloro-
trihydroxy biphenyl was only observed when the starting
material was at a high level of [2,4-DCP] (no dimer was
observed for 2,4-D), it could be concluded that
dimerization is possible only when the 2,4-DCP radicals
and CHQ radicals are simultaneously present at high
concentrations.
In addition to the dominant 2,4-DCP pathway,
several competitive reaction pathways coexisted in the
system and also contributed to the decay of 2,4-D,
including direct hydroxylation and the substitution of
chlorine atoms by HOd radicals. The resulting inter-
mediates, as mentioned before, were identied to be 5-
OH-2,4-D, 6-OH-2,4-D, 2-Cl-4-OH-PAA, and 4-Cl-2-
OH-PAA. The hydroxylation products of 2,4-D were
isomers of 5-OH-2,4-D, and 6-OH-2,4-D. It is believed
that 6-OH-2,4-D was the dominant species because the
addition of HOd occurs more favourably on the free
ortho-position than the meta-position of the aromatic
ring. Another pathway of 2,4-D transformation was the
substitution of chlorine by OHd radicals to yield two
isomers of 2-Cl-4-OH-PAA and 4-Cl-2-OH-PAA, which
may undergo consecutive hydroxylation leading to
chlorodihydroxyphenoxyacetic acid and chlorotrihy-
droxyphenoxyacetic acid, respectively.
Given that the total yield of the hydroxylation of 2,4-
D on C5 and C6 (5-OH-2,4-D and 6-OH-2,4-D) is higher
than that of the chlorohydroxyphenoxyacetic acids (2-
Cl-4-OH-PAA and 4-Cl-2-OH-PAA), the hydroxyl
radical is likely to tend to attack unoccupied sites rather
than substitute the chlorine on the aromatic rings
because the electron-withdrawing properties of Cl atoms
make the chlorinecarbon bond less favorable to attacks
by electrophilic HOd radicals (Antonaraki et al., 2002).
4. Conclusions
The nal oxidation capacity of FHU and FOHU was
dominated by the initial concentration of H2O2. The use
of highly photosensitive ferrous oxalate complexes
effectively promoted the production of hydroxyl radicals
and therefore improve the initial decay rates of 2,4-D.
The degradation pathways of 2,4-D by either the FHU
or FOHU process occurred mainly through the hydro-
xylation of the aromatic ring, the substitution of
chlorine by HOd, the substitution of CH2OHCOOH
by HOd, and the dehydrogenation of chlorinated
hydroquinone to the corresponding quinone upon
attacks by radicals. Eventually, the oxidation of quinone
and other hydroxylated products will result in the
formation of simple organic acids as the end products.
Acknowledgments
The work described in this paper was fully supported
by a grant from the University Grants Council of the
Hong Kong Polytechnic University.
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