Wat. Res. Vol. 35, No. 8, pp.

1994–2002, 2001
# 2001 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(00)00460-7 0043-1354/01/$ - see front matter

DEGRADATION OF 2,4-DICHLOROPHENOL
BY IMMOBILIZED IRON CATALYSTS
S. SABHI and J. KIWI*
Institute of Physical Chemistry II, Swiss Federal Institute of Technology (EPFL), 1015 Lausanne,
Switzerland

(First received 23 May 2000; accepted in revised form 9 August 2000)

Abstract}The degradation of 2,4-Dichlorophenol (from now on 2,4-DCP) has been carried out on
Nafion–Fe (1.78%) in the presence of H2O2 under visible light irradiation. A solution containing 2,4-DCP
(TOC 72 mg C/L)) is seen to be mineralized in
1 h in the presence of H2O2 (10 mM) under solar simulated
visible light (80 mW cm2) at pH values between 2.8 and 11. Homogeneous photo-assisted Fenton
reactions were capable of mediating 2,4-DCP degradation only up to pH 5.4. The degradation kinetics of
2,4-DCP on Nafion–Fe membranes was more favorable than the one observed during Fenton photo-
assisted processes at pH 2.8. The degradation of 2,4-DCP was investigated as a function of the substrate,
oxidant concentration and applied light intensity. The Nafion–Fe was seen to be effective over many cycles
during the photo-catalytic degradation of 2,4-DCP showing an efficient and stable performance during
2,4-DCP degradation without leaching out Fe3+-ions into the solution. Evidence is presented that the
degradation at the surface of the Nafion–Fe membrane seems to be controlled by mass transfer and not by
chemical reaction of the species in solution. The approach used to degrade 2,4-DCP is shown to be valid
for other chloro-carbons like 4-chlorophenol, 2,3-chlorophenol and 2,4,5-trichlorophenol. # 2001 Else-
vier Science Ltd. All rights reserved

Key words}2,4-DCP degradation and photo-degradation, immobilized Fenton catalysis, chlorophenols

degradation

INTRODUCTION leading to important additional OH-radicals in

To find better ways to mineralize pollutants of the
halocarbon family is a topic of timely interest due to
the increased availability of these type of compounds
in water bodies and their known toxic and carcino-
genic effects (Halmann, 1996). Halocarbons represent
the most abundant family of industrial toxic com-
pounds as it has been recently recognized from
different polluting sources like herbicides, pesticides,
chemical and solvent manufacturing and the paint
industry (Bauer et al., 1999). The application of
innovative Advanced Oxidation Technologies
(AOT’s) like the one presented in this study is of
interest to abate efficiently and also reduce the
treatment cost through destructive techniques miner-
alizing the halocarbon. Fenton processes have been
used as a powerful source of oxidative radicals
generating OH-radicals from H2O2 in the presence
of added Fe3+-ions (Walling, 1975). This process has
been shown recently to be enhanced by light due to
the decomposition of the photo-active Fe(OH)2+
*Author to whom all correspondence should be addressed.
Tel.: +41-21-693-3621; fax: +41-21-693-3621; e-mail:
john.kiwi@epfl.ch
1994
solution (Ruppert et al., 1993; Nadtochenko and
Kiwi, 1998). This is due to Fe2+ cyclic regeneration
in solution through the light induced reaction
FeðOHÞ2þ þ hn ! Fe2þ þ OH ð1Þ
3+
But Fe /H2O2 homogeneously catalyzed reactions
need up to 50–80 ppm of Fe-ions in solution which is
well above the European Economic Community
directives allowing 2 ppm Fe3+ in treated water to
be discharged directly into the environment (EEC,
1982). To remove sizable amounts of Fe-ions from
solution at the end of the treatment, precipitation
and re-dissolution of the Fe-ions are necessary with
the added cost in chemicals and labor.
To avoid this two drawbacks, Nafion1 perfluori-
nated membranes have been recently developed
where the Fe-ions cluster have been fixed and remain
active in H2O2 decomposition (Fernandez et al.,
1999). These membranes have been reported to resist
attack by the highly oxidative radical (OH/OH E8
1.90 V NHE) and do not allow leaching out of the Fe
exchanged on the sulfonic Nafion groups within the
3000 h testing period.
The compound under study (2,4-DCP) is a key
intermediate in the synthesis of the herbicide 2,4-D
 Chlorophenols degradation on Nafion–Fe films
(2,4-dichlorophenoxyacetic acid). The chloro-
aromatic under study has been reported to have a
removal rate 515 (mg g1 h1). It is considered
not degradable by acclimated mixed culture (Pitter
and Chudoba, 1991) enabling the 2,4-DCP to go
through waste water treatment stations without being
abated.
Since 1992 several studies involving illuminated
TiO2 suspensions of 2,4-DCP have appeared in the
scientific literature (Ku and Hsieh, 1992; Minero et
al., 1995; Malato et al., 1997; Jardim et al., 1997;
Giménez et al., 1999). The degradation of 2,4-DCP
by way of Fenton reactions has been reported some
time ago in closed reaction vessels (Barbeni et al.,
1983) and later by coupled chemical–biological
Fenton reactions focusing on the nature of the
bacterial species of the biological ensuing 2,4-DCP
destruction (Koyama et al., 1995).
The present study intends (a) to investigate the
solution parameters intervening in the degradation of
2,4-DCP at a kinetic acceptable rate by Nafion–Fe
(1.78%), (b) to compare the degradation of 2,4-DCP
with Fenton photo-assisted homogeneous processes,
(c) to see the influence of the variables during the
degradation mediated by Nafion–Fe (1.78%) in
solution, (d) to see whether the degradation of 2,4-
DCP on Nafion–Fe (1.78%) can be carried out at
more favorable pH values than in the homogeneous
Fenton case in view of ulterior biological treatment
and finally (e) to see if the Nafion–Fe (1.78%) can be
used advantageously in the case of chlorophenols
other than the 2,4-DCP chosen as model compound.
MATERIALS AND METHODS
Chemicals
The FeCl3, H2O2, acid, bases and chlorophenols in this
study were p. a. and used as received.
Membrane preparation
Experiments were conducted with Nafion-perfluorinated
membrane (Dupont 117, 0.007 in. thick, Aldrich #7.467-4)
containing hydrophilic sulfonate groups immobilized on the
fluorocarbon matrix. An improved procedure was used
compared to the one reported recently by our laboratory
(Fernandez et al., 1999) consisting of three steps: (a) The
Nafion membrane was washed with H2O2 (10%) and
subsequently with H2SO4 (5 N) to get a perfectly transparent
material, (b) this membrane is immersed in FeCl3 (0.1 M)
for 30 min and washed repeatedly until all Fe3+ and Cl-ion
are removed and (c) the membrane is immersed in NaOH
(0.01 M) for 30 min to convert the exchanged Fe3+ to its
hydrated form.
The Fe-content in the Nafion was determined after
digesting the membrane in concentrated HNO3 (Teflon-
coated autoclave) under pressure and temperature. This
solution was subsequently diluted and the Fe-content
measured by atomic absorption spectroscopy (AAS) in a
Philips 20 AS instrument provided with a flame detector.
The membranes used throughout this work had a loading of
1.78% by weight.
Photoreactor and irradiation procedures The irradiation
vessels used were 60 ml cylindrical Pyrex flasks (cutoff
1995
l  290 nm) each containing 40 ml of reagent solution. The
Suntest solar simulator had an intensity of 80 mW cm2
(
1.6 photons s1 cm2) within the wavelength range of 290
and 800 nm. The short wavelength UV radiation from the
Suntest solar simulator (l5310 nm) was removed from
reaching the samples by the Pyrex wall of the reaction
vessels. The radiant flux reaching the solutions in the
photolysis vessels (60 ml Pyrex) was set at 50 and
80 mW cm2. The Suntest lamp had a wavelength (l)
distribution with about 7% of the emitted photons
between 290 and 400 nm. The profile of the photons
emitted between l ¼ 400 and 800 nm followed closely the
solar spectrum. The radiant flux in mW cm2 was measured
with a power meter of LSI Corp, Yellow Springs, CO,
USA.
The Nafion catalysts strips of 48 cm2 were placed
immediately behind the wall of the reaction vessel to act
as the only light absorber in this two-phase system.
Analysis of the irradiated solutions The detection of the
dissolved iron in solution was carried out complexing
Fe-ions with cyanate (Fernandez et al., 1999).
Spectrophotometric analyses and degradation
measurements of the solutions were carried out by way of
a Hewlett-Packard 8452 diode array spectrophotometer.
The total organic carbon (TOC) was monitored via a
Shimadzu 500 instrument equipped with an ASI automatic
sample injector.
Modeling
The modeling of the interacting species in the solution
was carried out via the Acuchem IV program written by
Braun, Herron, Kahaner (National Bureau of Standards,
GA, Md 20899). The fitting was carried out with a program
written of the MatLab 4.2 by Volker and Hug of EAWAG
(Zürich) in conjunction with Acuchem software. The
ChemEQL (version 2.0) Program used was written by Beat
Mueller, Kastanienbaum, Switzerland. The ionization of
2,4-DCP as a function of pH was calculated using the pKa
values in equation (3) to compute at each pH value the
ionized fraction via the ChemEQL program.
RESULTS AND DISCUSSION
Degradation of 2,4-DCP solutions by way of photo-
assisted Fenton reactions
Figure 1 shows the spectra of 2,4-DCP in the
presence of various concentrations of Fe3+-ions. The
increase in optical density in Fig. 1 is due to the
increasing concentrations of Fe3+-ions. But no
overall changes in the absorption spectrum of 2,4-
DCP with a peak at l ¼ 285 nm were observed since
no complex formation between Fe3+ and 2,4-DCP
occurs.
Figure 2 shows the TOC reduction in mg C/L of
2,4-DCP during photo-assisted Fenton reactions at
different initially pH values. It is readily seen that
reactions proceed only up to pH 5.4. These results are
consequent with the observations that accelerated
Fenton-mediated degradations of chlorocarbons
proceed in acid media (Bauer et al., 1999; Halmann,
1996). The observed rate of 2,4-DCP destruction in
the presence of H2O2 alone was 55% compared with
the rate of photo-degradation observed in the
presence of Fe3+ as reported in Fig. 2.
1996 S. Sabhi and J. Kiwi

Fig. 1. Absorption spectra of 2,4-DCP solutions (1 mM) at pH 5.4 as a function of added concentration of
FeCl36H2O.

Fig. 2. Degradation of 2,4-DCP (1 mM) as a function of pH in the presence of FeCl3 (0.46 mM

or 26 mg Fe3+ L1) and H2O2 (10 mM) under Suntest irradiation (80 mW cm2) in homogeneous
solution.
 Chlorophenols degradation on Nafion–Fe films
The overall stochiometry of 2,4-DCP mineraliza-
tion reported in Fig. 2 can be stated as
HO2C6 H3 2Cl2 þ 4  OH þ 5O2
! 6CO2 þ3H2 O þ 2HCl ð2Þ
The ionization of 2,4-DCP as a function of pH is
shown in Fig. 3. The matrix takes into consideration
the pKa value of 7.85 for the deprotonation of the
2,4-DCP OH-group. This is the intersection point in
Fig. 3. Up to pH 7.95, the 2,4-DCP (denoted by HL)
is the dominating species in solution and above this
pH the L form predominates according to the
equilibrium
HL Ð Hþ þ L ð3Þ
Degradation of 2,4-DCP on Nafion–Fe membranes.
Cyclic nature of the process
Figure 4 presents the results of the degradation of
2,4-DCP solutions on Nafion–Fe (1.78%) mem-
branes in the dark and under light irradiation in
the presence of H2O2 as shown respectively in traces
6 and 7. If H2O2 is added to solutions of 2,4-DCP no
mineralization was observed as seen in traces 1 and 2.
Photolysis of 2,4-DCP does not lead to the photo-
Fig. 3. Distribution of 2,4-DCP species in solution as a function of pH.
1997
degradation of this halocarbon (trace 3). Nafion–Fe
membranes in the absence of H2O2 were seen to be
ineffective in 2,4-DCP degradation (traces 4 and 5).
The results presented in Fig. 4 indicate that only
Nafion–Fe membranes in the presence of H2O2 under
light irradiation were effective in the degradation of
2,4-DCP in kinetically acceptable times since they
were able to overcome the non-degradable inter-
mediates formed under the same experimental con-
ditions in the dark.
Fig. 5 shows the catalytic nature of the abatement
of 2,4-DCP carried out under the experimental
conditions reported in Fig. 4 (trace 7). At the end
of each cycle the halocarbon and H2O2 are added to
the solution and the irradiation with the Suntest is
carried out again. These results show the catalytic
nature of the degradation reaction on the Nafion–Fe
membrane.
pH variation observed during 2,4-DCP degradation.
Mechanistic and practical implications
Figure 6 presents the results of the degradation of
2,4-DCP in the presence of H2O2 under Suntest light
irradiation. It is seen that (a) in a wide pH-range the
photo-degradation is possible and (b) the kinetics
and efficiency of the photo-degradation are about the
1998 S. Sabhi and J. Kiwi
same within the pH range 2.8–11. This experimental
result differs considerably from the experimental
results presented in Fig. 2 showing that in homo-
geneous systems the photo-degradation proceeds
Fig. 4. Degradation of 2,4-DCP solutions. Initial pH 5.4.
Suntest irradiation (80 mW cm2) where pertinent. The full
points refer to dark degradations and the open points relate
to photo-catalytic reactions. In traces 1 and 2 only H2O2
(10 mM) has been added to 2,4-DCP solutions. Trace 3
shows photolysis of 2,4 DCP. Traces 4 and 5 show 2,4-DCP
solutions in the presence of Nafion–Fe membranes without
addition of H2O2. Traces 6 and 7 show the degradation of
the complete system: 2,4-DCP, Nafion-membrane and H2O2
(10 mM).
Fig. 5. Catalytic decomposition of 2,4-DCP in the presence of H2O2 (10 mM) at an initial pH 5.4 under
Suntest irradiation (80 mW cm2).
only up to pH 5.4 under with a much slower kinetics.
The nature of the catalysis and the intermediates in
Nafion–Fe membranes (Fernandez et al., 1999;
Balanosky et al., 1999) seems to be different
compared to homogeneous Fenton processes (Nad-
tochenko and Kiwi, 1998; Pignatello et al., 1999).
Figure 7 present the shift of pH of 2,4-DCP
solutions with a different initial pH under Suntest
light irradiation. The degradation is mediated by the
Nafion–Fe membrane in the presence of added H2O2.
The pH values coalesce after about 1 h reaction to a
value of around 4. The shift of the initial solution
without any pH adjustment is seen to move to more
acidic values. This pH drop from 5.4. to 4.0
corresponds to an increase in the [H+] concentration
by a factor >13. This pH change suggests the
generation of HO2 radicals
Fe3þ þ H2 O2 ! Fe2þ þ HO2  þ Hþ ð4Þ
The superoxyde radical HO2 in equation (4)
has a one-electron standard potential HO2/
O2 E8 ¼ 0:75 V vs NHE and the active form in
solution of this radical is HO2 since the pKa of HO2
is 4.8
HO2  Ð Hþ þO
2 pKa ð4:8  0:1Þ ð5Þ
A channel responsible for the increased acid char-
acter of the solution during degradation has already
been mentioned in equation (2). In addition Fig. 7
shows the pH during the degradation coalesces to a
pH
4 after about 1 h reaction for the different initial
solution pH values tried. The HO2 in equation (5) is
suggested as a radical species in solution during
 Chlorophenols degradation on Nafion–Fe films
Fig. 6. Degradation of 2,4-DCP solutions under Suntest light irradiation as a function of initial pH in the
presence of Nafion–Fe (1.78%) and H2O2 (10 mM).
2,4-DCP oxidation through its dissociated form at
pH>4.8. But this not the only oxidative radical
species present in the solution. Within 1 h most of the
2,4-DCP is mineralized as seen from Fig. 6.
The rather complex shape of the degradation as a
function of time in Fig. 7 also suggests the presence
of pH dependent Fe-aqueous complexes with differ-
ent structures and reactivity. The results presented
in Fig. 7 suggests species like: Fe(H2O)5(OH)2+,
Fe(H2O)4(OH)+ +
2 and [Fe2(H2O)4(OH)2 ] to be pre-
sent in solution at pH>3 (Gallard et al., 1999). The
degradation of 2,4-DCP on immobilized Nafion–Fe
systems has the advantage of avoiding the costly
initial pH adjustment to acidic pH values required
during the homogeneous Fenton degradation of
phenols (Ruppert et al., 1993; Halmann, 1996). For
the coupling of the pretreated solutions of 2,4-DCP
with low cost biological degradation, the adjustment
to pH-values ranging from 6 to 8 is still necessary but
=dt ¼ k½c
½HO2 
ð7Þ
the initial step involving costly acidification is not
necessary.
Dependence of the photo-degradation rate on 2,4-DCP
concentration
Figure 8 presents the decrease in TOC of 2,4-DCP
mediated by Nafion–Fe membranes at four different
halocarbon concentrations. The inset presents the
decrease in optical absorbance at the 2,4-DCP peak.
The steeper decline in TOC at higher concentrations
is due to the mass transfer taking place between 2,4-
DCP in solution and the membrane surface during
1999
the degradation process. In this case the mass
transfer between solution and the Nafion–Fe mem-
brane will be directly proportional to the difference in
2,4-DCP concentration existing in the diffusion layer
between the bulk of the solution and the membrane
interface. The diffusion distance (x) of the HO2-
radical away from the Nafion–Fe membrane can be
estimated from the Smoluschoski diffusion relation.
x2 ¼ Dt ð6Þ
Taking the approximate values in equation (6) of
D  105 cm2 s1 and t109 s for the HO2 or any
other oxidative radical (s), a diffusion distance of
1 nm can be estimated for the diffusion layer.
Supposing that the concentration of radicals away
from the Nafion–Fe follows a smooth function, the
decrease in the concentration of radicals can be
estimated from the relation
d½oxid  rad
Substituting the numerical values in equation (7)
of the radicals (c  1012 M) with 2,4-DCP
(c ¼ 0:25 mM) and assuming the diffusion controlled
rate k  6  109 M1 s1 (Halmann, 1996), then
d[oxid-rad]/dt can be estimated at
1.5  106 M s1.
Influence of the H2O2 concentration and the intensity
of the applied light during 2,4-DCP degradation
Figure 9 presents the photo-degradation of 2,4-
DCP under Suntest light irradiation mediated by the
Nafion–Fe membrane. The abatement of 2,4-DCP is
2000 S. Sabhi and J. Kiwi

Fig. 7. Shift of solution pH during Nafion–Fe mediated photo-degradation of 2,4 DCP in a solution H2O2
(10 mM) under Suntest light irradiation.

Fig. 8. Degradation of different concentrations of 2,4-DCP as a function of time in solutions with an

initial pH 5.4 irradiated with a Suntest (80 mW cm2) in the presence of H2O2 (10 mM). The optical
absorption for the different 2,4-DCP concentrations is shown in the inset.
 Chlorophenols degradation on Nafion–Fe films
Fig. 9. Degradation of 2,4-DCP as a function of H2O2
concentration in the presence of Nafion–Fe membrane
under Suntest light irradiation. The concentrations of H2O2
used are noted in the figure captions.
Table 1. Photodegradation of chlorophenols mediated by Nafion–Fe membranes under Suntest light irradiation in the presence of H2O2
(10 mM)
Chloro-compound Initial TOC
Light exposure: Suntest 80 mW cm2
4-Chlorophenol 73
2,3-Dichlorophenol 74
2,4,5-Trichlorophenol 72
Dark exposure
4-Chlorophenol 71
2,3-Dichlorophenol 75
2,4,5-Trichlorophenol 68
more favorable as the concentration of the oxidant
increases in solution. The visible light of the Suntest
irradiator was adjusted to values of 50 and
80 mW cm2. The TOC decrease was faster in the
second case confirming the influence of the intensity
of the applied light on the degradation rate.
Photodegradation of other chlorophenols on Nafion–Fe
membranes
Figure 10 presents the degradation of some model
chlorophenols as a function of time under Suntest
light irradiation on Nafion–Fe membranes. The
degradation kinetics is seen to be very close for the
three chlorophenols presented in Fig. 10. These
results lend support to the claim that Nafion–Fe
membranes in oxidative media are capable of
degrading different chlorophenols with about the
same kinetics and independently of the Cl-substitu-
2001
Fig. 10. Photo-degradation of 4-chlorophenol (4-CP); 2,3-
chlorophenol (2,3-DCP) and 2,4,5-trichlorophenol (2,4,5-
TCP) mediated by Nafion–Fe in solutions with H2O2
(10 mM) under Suntest irradiation. Full points refer to
experiments in the dark and open points are the results of
experiments under light irradiation.
Exposure (h) Decomposition (%)
2 90
2 90
2 90
2 35
2 34
2 25
ents of the particular halocarbons as observed during
the photo-catalytic degradation mediated by TiO2
dispersions (Halmann, 1996; Barbeni et al., 1998).
More important was the observation that the three
chlorophenols degraded with about the same kinetics
within the pH range under the conditions used in Fig.
10. This result is close to the result reported in Fig. 6
for 2,4-DCP and may be useful for degradations at
biological pH. Results in Table 1 show the effect of
light on the decomposition of the three halocarbons
and phenol taken as reference compound after a 2 h
irradiation period.
CONCLUSIONS
The Nafion–Fe catalytic membrane used to de-
grade 2,4-DCP during this study shows adequate
kinetics and chemical stability during long-term
2002 S. Sabhi and J. Kiwi
operation. The degradation kinetics when Nafion–Fe
membranes were used was similar and even faster
than in the case of homogeneous photo-assisted
Fenton reactions. The Nafion membrane showed
stable performance during long-term repetitive cata-
lytic cycles. In the absence of visible light irradiation,
the degradation intermediates seem to preclude
further degradation of 2,4-DCP in solution. Na-
fion–Fe mediated photo-catalysis allows to carry out
the degradation up to pH 11 avoiding the costly pH
adjustment necessary during homogeneous photo-
assisted Fenton degradation. The degradation of 2,4-
DCP seems to be controlled by mass transfer as
shown by the dependency of the TOC values as a
function of the initial 2,4-DCP concentration. An
estimate for the width of HO2-radical diffusion layer
next to the membrane is presented. The influence of
the oxidant concentration and the applied light
intensity on the degradation of 2,4-DCP have also
been investigated.
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