Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 83:13231338 (2008)

Review
An overview of the application of Fenton
oxidation to industrial wastewaters treatment
P Bautista, A F Mohedano, J A Casas, J A Zazo and J J Rodriguez
Ingeniera Qumica, Universidad Autonoma de Madrid, Crta. de Colmenar Km.15, 28049 Madrid, Spain

Abstract: This review provides updated information on the application of the Fenton process as an advanced
oxidation method for the treatment of industrial wastewaters. This technology has been used in recent decades
as a chemical oxidation process addressed to meet a variety of objectives including final polishing, reduction of
high percentages of organic load in terms of chemical oxygen demand or total organic carbon and removal of
recalcitrant and toxic pollutants thus allowing for further conventional biological treatment. The efficiency and
flexibility of this technology has been proven with a wide diversity of effluents from chemical and other related
industries or activities, including pharmaceutical, pulp and paper, textile, food, cork processing, and landfilling
among others.
2008 Society of Chemical Industry

Keywords: Fenton process; chemical oxidation; industrial wastewaters treatment; waste minimization; leachate

INTRODUCTION reaction of Fe3+ with intermediate organic radicals

Industrial activities generate wastewaters with a (Equations (3)(5)):2 6
wide variety of contaminants, such as phenol and
derivatives, hydrocarbons, halogenated sulphur and Fe2+ + H2 O2 Fe3+ + HO + HO
nitrogen-containing organic compounds, heavy metals
in the form of cyanides and other organic complexes. k = 76 L mol1 s1 (1)
+
Frequently these wastewaters contain a mixed pool Fe 3+
+ H2 O2 Fe 2+
+ HO2 + H
of pollutants in a wide range of concentrations. The
development of cost-effective technical solutions is k = 0.01 L mol1 s1 (2)
needed to successfully deal with the increasingly RH + HO R +H2 O (3)
complex problems arising in the field of industrial
wastewaters. R +Fe3+ R+ + Fe2+ (4)
+
In recent decades, chemical treatment methods R + HO R-OH (5)
involving the generation of hydroxyl radicals, known
as advanced oxidation processes (AOPs), have been Nevertheless, a number of competitive reactions
applied successfully for the removal or degradation can also occur (Equations (6)(9)), which negatively
of recalcitrant pollutants based on the high oxidative affect the oxidation process:
power of the HO radical.
Among these AOPs, the Fenton process is a widely Fe2+ + HO Fe3+ + HO
studied and used catalytic method based on the
k = 3.2 108 L mol1 s1 (6)
generation of hydroxyl radicals (HO) from hydrogen
peroxide with iron ions acting as homogeneous catalyst H2 O2 + HO HO2 +H2 O
at acidic pH and ambient conditions.1 The HO
k = 2.7 107 L mol1 s1 (7)
radical has a high standard oxidation potential (2.80 V)
and exhibits high reaction rates compared with other HO2 +HO O2 + H2 O (8)
conventional oxidants like Cl2 , O2 , O3 , hydrogen
HO +HO H2 O2
peroxide or KMnO4 . This radical reacts with most
organic and many inorganic solutes with high rate k = 5.2 109 L mol1 s1 (9)
constants.
The generally accepted mechanism of the Fenton The rate of the Fenton reaction should be
process proposes that hydroxyl radicals are produced strongly dependent on the presence of radical
in accordance with Equation (1), while the catalyst scavengers such as t-butanol or chlorine ions,
is regenerated through Equation (2), or from the but in some cases, a substantial decrease has

Correspondence to: J J Rodriguez, Ingeniera Qumica, Universidad Autonoma de Madrid, Crta. de Colmenar Km.15, 28049 Madrid, Spain
E-mail: juanjo.rodriguez@uam.es
(Received 14 March 2008; revised version received 25 April 2008; accepted 28 April 2008)
Published online 6 June 2008; DOI: 10.1002/jctb.1988

2008 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2008/$30.00

P Bautista et al.
not been observed even at high concentrations
of these species.7 This fact led some authors to
analyze the presence of additional oxidant species.
Using electron paramagnetic resonance (EPR)-spin
trapping techniques, experimental evidence has been
found for the existence of oxidizing intermediates
different from the hydroxyl radical,8 11 such as high-
valent iron-complexes (e.g. ferryl species Fe(IV),
denoted as Fe(OH)2 2+ ; Equation (10)). Depending
on the operating conditions (substrate, Fe/H2 O2 ratio,
scavengers, etc.) one of them will predominate.
Fe2+ + H2 O2 Fe(OH)2 2+
Fe3+ + HO +HO
Whereas the hydroxyl radical reacts by hydrogen
abstraction, addition to double bonds or electron
transfer, depending on the structure and especially
on the ionization potential of the organic pollutant,
the ferryl species are only able to oxidize organic
molecules by electron transfer.
The efficiency of the Fenton oxidation process
depends, among other factors, like temperature, pH,
hydrogen peroxide and catalyst concentrations, on the
Fe3+ reduction to Fe2+ . Thus the presence of reaction
intermediates able to reduce Fe3+ and regenerate
the catalyst is crucial.3 However, there are reaction
intermediates that instead of reducing the Fe3+ remove
it from the Fe2+ /Fe3+ cycle, due to the generation
of iron complexes, delaying and/or inhibiting the
oxidation process.
Fenton reaction presents its maximum catalytic
activity at pH 2.83.0, which drastically diminishes
with an increase or a reduction of this pH value. At pH
higher than 3 Fe3+ starts precipitating as Fe(OH)3 and
breaks down the H2 O2 into O2 and H2 O preferently.12
Besides, the formation of Fe(II) complexes at high pH
values leads to a drop of the Fe2+ concentration.13 On
the other hand, Fe2+ regeneration by the reaction of
Fe3+ with H2 O2 is inhibited at more acidic pH values.4
H2O2
Fe(SO4)7H2O
pH adjusting
agent
pH
Raw wastewater control
Oxidation
tank
Figure 1. Typical scheme for Fenton treatment.
1324
The reaction temperature is another crucial param-
eter in the Fenton process. In principle, increasing the
temperature should enhance the kinetics of the pro-
cess, but it also favours the decomposition of H2 O2
towards O2 and H2 O, whose rate increases around 2.2
times each 10 C in the range 20100 C.14
The dose of H2 O2 and the concentration of Fe2+
are two relevant factors affecting the Fenton process,
being both closely related. The H2 O2 dose has to be
fixed according to the initial pollutant concentration. It
is frequent to use an amount of H2 O2 corresponding
to the theoretical stoichiometric H2 O2 to chemical
oxygen demand (COD) ratio,15 although it depends on
the response of the specific contaminants to oxidation
(10) and on the objective pursued in terms of reduction of
the contaminant load.
A schematic representation of the Fenton oxidation
treatment is shown in Fig. 1. Typically a stirred batch
reactor is used where the pH is controlled commonly
within the 33.5 range. Fe2+ is most frequently
added as ferrous sulphate and H2 O2 is usually fed
as 35% aqueous solution. The process usually works
at ambient temperature and pressure. The reactor
vessel must be coated with an acid-resistant material,
because corrosion can be a serious problem. Addition
of reactants is performed in the following sequence:
wastewater, followed by dilute sulphuric acid (for
maintaining acidic conditions), the catalyst (Fe2+ salt)
in acidic solution, base or acid for pH adjustment
and finally hydrogen peroxide. The discharge from
the Fenton reactor passes to a neutralization tank
and after flocculant addition the Fe(OH)3 and other
accompanying solids are separated by settling. If
necessary, a final sand-filtration stage can be used.
One of the advantages of the Fenton process with
regard to other oxidation techniques is that no energy
input is necessary to activate hydrogen peroxide,
because the reaction takes place at atmospheric
pressure and at room temperature. Furthermore, this
method requires relatively short reaction times and
uses easy-to-handle reagents. The main disadvantages
Alkaline
agent Flocculant
pH
control
Treated wastewater
Neutralization Flocculation
tank tank
Settling tank
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb

are the high cost of hydrogen peroxide and the fact
that the homogeneous catalyst, added as iron salt,
cannot be retained in the process thus requiring further
separation to prevent additional water pollution. In
order to avoid the continuous loss of catalyst and
the need of removing iron after the treatment, which
increases the cost, heterogeneous catalysts can be
used. Recent studies have shown that hydrogen
peroxide can oxidize organic pollutants in the presence
of Fe-bearing solid catalysts. Zeolites,16 23 pillared
clays,24 28 alumina,29 silica,30 mesostructured SBA-
15,31,32 mesoporous molecular sieves,33,34 niobia,35
iron oxides,36,37 ion-exchange resin38 and activated
carbon39,40 have been used as supports to prepare the
catalysts.
APPLICATION OF FENTON OXIDATION TO
INDUSTRIAL WASTEWATERS
Fenton oxidation has been tested with a variety of
synthetic wastewaters containing a diversity of target
compounds, such as phenols,41 44 chlorophenols,45 48
formaldehyde,49 2,4-dinitrophenol,50,51 2,4,6-trinitro-
toluene,52,53 2,4-dinitrotoluene,54 chlorobenzene,55,56
tetrachloroethylene,57 halomethanes,58 amines,59 he-
xahydro-1,3,5-trinitro-1,3,5-triazine (RDX).60,61
However, there are many chemicals which are refrac-
tory to Fenton oxidation, such as acetic acid, acetone,
carbon tetrachloride, methylene chloride, oxalic acid,
maleic acid, malonic acid, n-paraffins, trichloroethane,
etc.62 It has been demonstrated that these compounds
are resistant under the usual mild operating conditions
of Fenton oxidation.2,28,40,44
In addition to those basic studies, the process has
been applied to industrial wastewaters (such as chemi-
cal, pharmaceutical, textile, paper pulp, cosmetic, cork
processing wastewaters, etc.), sludge and contamined
soils63 68 with the result of significant reductions of
toxicity, improvement of biodegradability, colour and
odour removal.
Chemical industry
The chemical industry is a major contributor to
the nowadays problem of industrial wastewaters,
not only in terms of discharge volumes, but also
looking at the hazardous nature of many of the
pollutants found in the effluents. The increasingly
stringent regulations have enforced the application of
advanced technologies for complying the discharge
limits and allowing for water recycling. Among those
technologies, Fenton oxidation has been gaining
interest in the last two decades.
Barbusinski and Filipek69 analyzed the efficiency of
the Fenton technology in the treatment of the wastew-
aters from pesticides production in southern Poland.
Most of the pesticides were completely degraded using
a H2 O2 dose of 2.5 g L1 , corresponding to five times
the stoichiometric amount on a COD basis. The
best results were achieved for the organophospho-
rous pesticides, which degraded at 97100%. The
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment
removal efficiency for organochlorinated was also fairly
high (>90%), and the toxicity of the raw wastewater
towards the bioluminescent bacteria Vibrio fischeri was
dramatically reduced.
In a further work, Barbusinski70 studied the
application of Fenton process for treating four types
of industrial wastewaters collected from two chemical
factories in southern Poland. The wastewaters came
from the production of maleic acid, maleic anhydride,
2-ethylhexyl alcohol, urea-formaldehyde adhesives
and pesticides. Although high removal efficiencies
were obtained in terms of COD, these were not
always accompanied by a reduction of ecotoxicity
(Vibrio fischeri) to sufficiently low levels unless
frankly high H2 O2 amounts and reaction times were
used.
A good example on the benefits of applying Fen-
ton oxidation to wastewaters from chemicals man-
ufacturing is reported by Collivignarelli et al.71 The
wastewaters from a detergents producing plant were
formerly treated by coagulationflocculation and fil-
tration, a solution which showed to be not capable
of reaching the purification requirements. A new
system consisting in a discontinuous Fenton oxi-
dation and neutralisation process, followed by floc-
culation and sedimentation was successfully imple-
mented.
Wastewaters from petroleum extraction, refin-
ing and chemical processing have been success-
fully treated with the Fenton system under ambi-
ent conditions of pressure and temperature.72
These authors tested the efficiency of this pro-
cess for the treatment of two different wastewa-
ter samples, one from oil production operations
and the other one from a petrochemical plants
complex. The treated contaminants, in harzadous
concentrations, were the following: m-cresol, 2-
chlorophenol, methyl-tertbutyl-ether (MTBE) and
volatile aromatics (benzene, toluene, ethylbenzene
and xylene). In all cases a significant mineraliza-
tion (namely, complete oxidation) of the contam-
inants was observed in relatively short periods of
time.
Acidizing, a technique for improving the permeation
ability of rock layers of petroleum wells using diluted
inorganic acids such as HCl, has long been one of
the most common ways of stimulation to increase
the production rate of oil and gas reservoirs. This
operation gives rise to about 200500 m3 waste acidic
liquid per well, containing high concentrations of HCl
and ferrous ions in addition to a high organic load. Gao
et al.73 analyzed the potential of the Fenton process
for the simultaneous removal of total organic carbon
(TOC) and Fe2+ from these acidic waste liquors,
by adding H2 O2 . The samples used in that study
were collected from an acidic waste liquor pond in
China, with main characteristics: pH = 1.4, 94 mg
L1 TOC and 208 mg L1 Fe2+ . The optimum molar
ratio of H2 O2 /Fe2+ for the removal of Fe2+ was
0.720.76, which was determined from the oxygen
1325
P Bautista et al.
reduction potential (ORP), used as a parameter
to indicate the transformation of the Fe3+ /Fe2+ .
Under this optimal H2 O2 dose, the minimum Fe2+
final concentration (1.21.3 mg L1 ) occurred at
45 min at 3.34.5 pH. TOC removal was affected by
oxidation as well as adsorption by ferric hydroxides
being dominated by adsorption at a molar ratio
H2 O2 /Fe2+ of 0.75, and by oxidation at a molar
ratio H2 O2 /Fe2+ of 3.0. In this latter case (380 mg
L1 H2 O2 ), more than three-quarters of the TOC
removal was due to oxidation, for a total TOC
reduction of 65% in 120 min, at room temperature
and pH = 3.25.
Leather tanning effluents are a source of severe
environmental impacts, since this industry generates
an alkaline wastewater with high concentrations of
organic matter, sulfides, suspended solids and salts,
which shows high toxicity values. The treatment of
these industrial wastewaters by combined chemical
and biological oxidation was evaluated by Vidal et al.74
In that study Fenton oxidation was used as batch pre-
treatment. The H2 O2 /Fe2+ and H2 O2 /COD ratios
were 9 and 4, respectively, reaching a COD reduction
close to 90%. Subsequently, the oxidized effluent was
fed to an activated sludge unit, reaching 3560% and
6070% of COD and BOD removal, respectively.
Therefore, this combined treatment increased the
overall COD removal up to more than 95% versus
the 60% attained without pre-treatment. Bioassays
with D. magna and D. pulex showed that this kind of
treatment achieves only a partial toxicity removal of
the tannery effluent.
Dantas et al.75 evaluated the efficiency of Fenton
and photo-Fenton processes for the treatment of
wastewaters from the leather industry, investigating
the reduction of COD, ammonia-N and toxicity.
The results obtained showed that the degradation
process involves two stages: an initial fast one,
where approximately 70% of the COD reduction
takes place, followed by a slow step, where after
4 h reaction time the COD removal reached 90%.
The efficiency of the Fenton and photo-Fenton
reactions increased from 65 to 90%, since the
concentration of HO radicals increases in the second
process. The toxicity (using Artemia salina) decreased
upon COD reduction but the residual H2 O2 at
the end of the reaction had to be controlled
because it affects negatively to the final toxicity
values.
The cosmetic industry generates wastewaters char-
acterized by high levels of COD, suspended solids, fats
and oils and detergents. The reduction of the organic
load of these effluents by conventional biological pro-
cesses is not likely due to its low biological oxygen
demand (BOD5 )/COD ratio and thus they are fre-
quently treated by means of coagulation/flocculation
with pressure-flotation to separate the resulting sludge.
This leads to an important reduction of COD. Never-
theless, the introduction of more stringent regulations
concerning public waste disposal makes necessary to
1326
develop new techniques for a more efficient cleaning
of this type of wastewaters. A possible strategy can
be the use of chemical oxidation as a previous treat-
ment in order to reduce the toxicity and improve the
biodegradability of the organic matter in these wastew-
aters. The removal of organic matter (TOC and COD)
by Fenton oxidation from two samples of wastewaters
generated in a cosmetic industry in Madrid (Spain)
has been evaluated by Bautista et al.76 These two
effluents contained significantly different values of
COD (4730 and 2660 mg L1 ). The corresponding
TOC values were 1215 and 785 mg L1 and the
BOD5 /COD ratio was 0.133 and 0.169, respectively,
indicative in both cases of a low biodegradability.
The best results, TOC conversion higher than 45%
at 25 C and 60% at 50 C, were obtained using an
initial pH equal to 3, a Fe2+ dose of 200 mg L1
and an initial H2 O2 /COD weight ratio corresponding
to the theoretical stoichiometric value. Application of
Fenton oxidation allowed compliance with the COD
regional limit for industrial wastewaters discharges to
the municipal sewer system. The overall kinetics of
the process was adjusted to a second-order kinetic
equation with respect to TOC. This simple equa-
tion described well the rate of TOC reduction over a
wide range covering up to 8090% of the maximum
achievable TOC removal.
A comparison of several AOPs was carried out with
a cosmetic industrial effluent by Coste et al.77 After
a complete biological treatment by membrane biore-
actor (BIOSEP) refractory COD still remained. Six
oxidation treatments were compared for COD reduc-
tion: Fenton reagent, direct photolysis with a low
pressure UV lamp, O3 at acidic pH and pH 6.25,
UV/O3 , UV/H2 O2 , O3 /H2 O2 and O3 /UV/H2 O2 . The
results obtained seem to indicate that the compo-
nents of the pre-treated effluent were removable by
radical mechanism, but a fraction needed UV pho-
tolysis to be completely oxidized. Fenton reagent
offered a maximum COD reduction of 80%, pre-
senting a fraction that may be more refractory to free
radicals oxidation perhaps due to scavengers competi-
tion.
Wastewaters from phenolic resins manufacture have
a high concentration of phenol and derivatives, which
are extremely toxic and refractory. Thus, treating
phenolic wastewaters up to harmless level is an ardu-
ous task for many biological and chemical processes.
Kavitha and Palanivelu78 evaluated the efficiency of
different Fenton-related processes, such as Fenton,
solar-Fenton and UV-Fenton, for the degradation of
phenol in simulated and industrial wastewaters. The
real effluent was taken from a resin-manufacturing
facility in India and contained 2904 mg L1 COD,
933 mg L1 dissolved organic carbon (DOC) and
1215 mg L1 phenol. Increased degradation and min-
eralization efficiencies were observed in photo-Fenton
processes as compared to conventional Fenton oxi-
dation. The optimum conditions were: room tem-
perature, pH = 3, H2 O2 /COD weight ratio of 2.2
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb

and Fe2+ /H2 O2 molar ratio of 0.026 for Fenton
and 0.013 for solar-Fenton. In both oxidation pro-
cesses phenol was removed effectively within 5 min
of reaction time. However, the degradation (COD)
and mineralization (DOC) efficiency of the Fenton
process were 82 and 41%, respectively, whereas in
solar-Fenton almost complete degradation and 97%
mineralization were achieved within 120 min of reac-
tion time.
Park et al.79 investigated the feasibility of Fen-
ton oxidation for the removal of colour and the
non-biodegradable organics from a wastewater from
pigment production. Batch tests were performed
in order to determine the optimum conditions
for plant operation, such as pH, H2 O2 dosage,
H2 O2 /Fe2+ molar ratio and contact time. The ini-
tial organic pollution of the raw wastewater was
2700 mg L1 of COD and it was found that the
removal efficiencies reached more than 90% and
around 50% for colour and COD, respectively. In
addition, the biodegradability of the effluent was sig-
nificantly improved by means of Fenton oxidation
since BOD5 /COD ratio was increased from 0.04 to
0.36.
Pharmaceutical industry
Treatment of pharmaceutical wastewaters has always
been troublesome owing to the wide variety of chem-
icals used in drug manufacturing, which leads to
wastewaters of variable composition and fluctua-
tions in pollutant concentrations. The substances
synthesized by the pharmaceutical industry are in
most cases structurally complex organic chemicals
that are resistant to biological degradation. For this
reason, conventional methods are usually inappropri-
ate for the treatment of pharmaceutical wastewaters
and advanced oxidation processes can be considered
good candidates for providing feasible technical solu-
tions.
Fenton oxidation has proved to be a suitable pre-
treatment for an extremely polluted pharmaceutical
wastewater with 362 000 mg L1 COD, mostly due to
recalcitrant compounds, as indicated by a BOD5 /COD
ratio as low as 0.008.80 The results reported by
these authors show that during the first 10 min of
Fentons reaction more than 90% of the total COD
removal (5560%) can be achieved. This finding is
of special interest for the industrial application of
Fenton technology, because it proves that it permits
a significant COD reduction in a fairly short period
of time. This advantage of the Fenton process with
respect to other advanced oxidation processes was
also pointed out by Hofl et al.81 , who compared
the efficiency of three AOPs (H2 O2 /UV, O3 /UV and
Fenton) for the removal of adsorbable organic halogen
(AOX) and COD from a pharmaceutical wastewater.
The results showed that the three methods are suitable
for the degradation of AOX and COD. UV irradiation
involved a high selectivity for the degradation of AOX
compared to COD. On the other hand, processes
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment
based on hydroxyl radicals were less selective but
considerably more effective in COD degradation. This
explains why the combined methods H2 O2 /UV and
O3 /UV led both to complete destruction of AOX
and high removal of COD. Using Fenton oxidation
both AOX and COD could be removed almost
completely, being the reaction time needed for this
treatment fairly low compared with the other two
AOPs.
Kulik et al.82 applied modified Fenton oxidation
(H2 O2 /Fe2+ system without pH adjustment) in com-
bination with lime coagulation for the treatment of
three rinsing wastewater samples from a pharmaceuti-
cal plant formulating medical ointments. All samples
were pre-treated by adsorption/flocculation/filtration
processes with bentonite, but the quality of effluents
did not comply with the regulations for wastewater
discharge to local sewerage, since the organic matter
content of the three effluents in terms of COD was
4000, 5400 and 13 130 mg L1 . The application of
Fenton-like oxidation with subsequent iron(III)/lime
coagulation substantially improved the quality and the
biodegradability of the pharmaceutical effluents with
different chemical characteristics allowing to meet the
discharge limits. The rapid pH decrease to acidic val-
ues 3 during the initial stage of the process for all the
effluents suggested that pH adjustment was unneces-
sary. Under the most favourable treatment conditions
(H2 O2 /COD weight ratio of 2:1, H2 O2 /Fe2+ molar
ratio of 10:1 and 2 h reaction time), COD removal of
87%, 94% and 96% and BOD7 removal of 79%,
92% and 95% were achieved for the three efflu-
ents.
Another example of industrial application of the
Fenton process for the treatment of pharmaceutical
effluents is reported by Tekin et al.83 In their study
Fenton oxidation is applied as a pre-treatment for
the wastewaters generated by a drug manufacturing
plant in Turkey, leading to an improvement of the
wastewater biodegradability and a reduction of the
toxicity of these effluents. Treatability studies were
conducted at lab scale with synthetic aqueous solutions
of each chemical produced in the factory in order
to establish the operating conditions for the full-
scale treatment plant. Optimum pH was found to
be 3.5 and 7.0 for the first (oxidation) and second
(coagulation) stage of the Fenton process, respectively.
The effect of temperature on COD removal was
tested at room temperature and at 50 C, and no
significant differences were observed. Similar results
were found by San Sebastian et al.80 with this type
of wastewater. The industrial treatment plant using
Fenton oxidation followed by aerobic degradation
in sequencing batch reactors (SBR), provided an
overall removal efficiency of 98% for both COD
and BOD5 , complying with the discharge regional
limits. The COD removal efficiency attained in the
Fenton oxidation unit ranged between 45% and
50%.
1327
P Bautista et al.
Pulp and paper industry
The pulp and paper industry is known to generate
considerable volumes of wastewaters, about 80 m3 t1
of paper on average. More than 250 chemicals
have been identified in the effluents resulting
from the different stages of papermaking. Whereas
some of these pollutants are naturally occurring
wood extractives (tannins, resin acids, lignin, etc.),
others are xenobiotic compounds that are formed
mostly in pulp manufacture (chlorinated lignins,
phenols, dioxins and furans, among others). These
effluents are highly coloured and contain high organic
loads, which in some cases can reach more than
10 000 mg L1 of COD.84 Primary clarification is
the most frequently used treatment for this type of
wastewaters, sometimes followed by secondary or
biological treatment. However, some drawbacks are
associated with these methods, such as the large area
required for aerobic biological treatment, the difficulty
of controlling the population of microorganisms
and the rigorous control of pH, temperature and
nutrients. Also, the presence of toxic or recalcitrant
compounds seriously limits the efficiency of biological
treatments.
The combination of Fenton and photo-Fenton
oxidation has proved to be highly effective for the
treatment of pulp bleaching effluents.85,86 Solar photo-
Fenton reduced TOC as much as 93% after 15 min
according to the results of these last authors.
As indicated before, Fe3+ can also be used to
decompose H2 O2 giving rise to oxidative radicals in the
so-called Fenton-like process. For most applications
no significant differences have been observed when
Fe2+ or Fe3+ ions were used to catalyze the reaction,
although Pera-Titus et al.87 suggested that if low
doses of Fentons reagent are used, ferrous ions may
be preferable. Tambosi et al.88 evaluated a Fenton-
like process (involving oxidation and coagulation)
for the treatment of a wastewater generated by a
Brazilian paper mill with the objective of reducing
COD, colour, odour and aromatic compounds. Batch
experiments were carried out in order to determine
the optimum operating conditions, which led to 75%
COD removal. Based on these optimum conditions,
pilot-scale experiments were conducted and revealed
a high efficiency in terms of mineralization, namely
complete oxidation. Some terpenes identified in the
starting wastewater were completely removed by the
Fenton-like treatment.
Perez et al.85 evaluated the efficiency of several
AOPs for colour and organic matter removal from
a cellulose bleaching effluent. The costs of the
different technologies per unit of TOC reduction were
compared. Fenton, Fenton-like and photo-Fenton
achieved higher levels of TOC reduction and at lower
costs than photocatalytic treatments.
Textile industry
Textile industry is particularly known for its high
water consumption as well as the amount and variety
1328
of chemicals used throughout the different opera-
tions. The environmental problems associated with
textile effluents are in a great part due to colour.
The biorefractory nature of textile wastewaters from
the dyeing and finishing stages is mainly attributable
to the extensive use of various dyestuffs and chem-
ical additives (such as polyvinyl alcohol, surfactants,
etc.). Therefore, the wastewaters are characterized by
a high organic matter content (COD, BOD5 ), sus-
pended solids, colour and pH values up to 2 in the
acid range and as high as 12 in the basic.12 Differ-
ent treatments have been used for the wastewaters
generated from textile dyeing. These include acti-
vated carbon adsorption, coagulationflocculation,
biological degradation (activated sludge), electro-
chemical treatment, ozonation, etc., which often
produce final effluents still exceeding the discharge
limits.
Several authors have successfully applied the
Fenton process for this kind of industrial effluents.
In this way, Flaherty and Huang89 evaluated the
efficiency of Fenton oxidation for the treatment
of four refractory dyeing wastewaters from a US
textile facility. Batch and continuous flow oxidation
experiments were carried out, resulting in a 60%
and 30% COD reduction, respectively. A significant
colour reduction was achieved in all the cases. In
addition, these authors performed some experiments
using Fe3+ (Fenton-like reaction) instead of Fe2+ ,
concluding again that Fe3+ has a catalytic effect
comparable to the traditionally used Fe2+ . They
suggested that FeCl3 or Fe2 (SO4 )3 would be the
most practical catalysts for industrial applications
of Fenton-like oxidation, due to their strong acidic
character.
Badawy and Ali90 analyzed the effectiveness of Fen-
ton oxidation for the combined treatment of industrial
wastewaters generated from textile, chemical, food
and metal finishing industries and domestic efflu-
ents from an Egyptian city. They compared the
efficiency of a conventional treatment based on coag-
ulationflocculation with the results obtained by the
use of Fenton oxidation. The industrial wastewaters
contained 17503323 mg L1 of COD, 9003000 mg
L1 of SS and 13.295.5 mg L1 of oil and grease
in addition to heavy metals. The organic pollutants
included refractory, non-biodegradable and toxic com-
pounds, such as the dyestuffs used by the textile indus-
try. The authors found that coagulationflocculation
has a poor effect on the removal of soluble organic
compounds such as reactive dyes. The best results
were obtained with the Fenton process, reaching
as much as 100% colour removal and more than
90% reduction of COD. The results proved that
Fenton oxidation could be used for the treatment
of such industrial wastewaters without further treat-
ment, since the final effluent complies with the
Egyptian law for water reuse under a restricted cate-
gory.
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb

The effectiveness of Fenton and ozone oxidation
have been compared with a coagulationflocculation
process to remove toxicity as well as colour and COD
from the wastewater generated by a textile finishing
industry located in Istanbul (Turkey).91 The operat-
ing conditions for each process were established on
the basis of complete removal of the toxicity to Daph-
nia magna. The results obtained indicate that Fenton
oxidation removes COD to a major extent (59%)
rather than O3 (33%), while colour removal was
similar (89% and 91%, respectively). The coagula-
tionflocculation treatment yielded COD and colour
removal close to those of Fenton oxidation, but it
produces a higher volume of sludge containing recal-
citrant compounds (dyes, additives, etc.). Although
the Fenton process was operated at a higher tem-
perature (40 C), this was not a drawback since the
temperature of the effluent to be treated was above
70 C.
Papadopoulos et al.92 examined the effectiveness
of Fenton oxidation for the reduction of the
organic content of the wastewater generated from
a textile industry in Athens (Greece). The ini-
tial organic pollution of the raw wastewater was
1200 mg L1 of BOD, 8100 mg L1 of COD and
3010 mg L1 of TOC. The low BOD/COD ratio,
0.148, indicates that this organic matter is non-
biodegradable. The experimental results showed that
the COD decreased by about 45% within 4 h
and a higher reaction time did not lead to fur-
ther significant COD reduction (48% overall reduc-
tion after 6 h). The maximum colour removal was
71.5%.
As indicated before, heterogeneous Fenton oxida-
tion is an interesting alternative to the traditional
homogeneous Fenton process. In this way, Dantas
et al.39 studied the treatment of a textile wastewa-
ter (COD = 1000 mg L1 ) in Santa Catarina State
(Brazil) by adsorption and simultaneous catalytic
wet hydrogen peroxide oxidation using composites
of iron oxide and activated carbon (Fe2 O3 /carbon).
They pointed out that no iron was leached to the
aqueous phase, indicating that the homogeneous Fen-
ton reaction was not significant and the catalyst is
fairly stable at pH above 3.0. Besides, a lower hydro-
gen peroxide consumption than in the homogeneous
Fenton process was needed, achieving 71% COD
removal at room temperature with a H2 O2 dose lower
than 1000 mg L1 (less than half the stoichiometric
amount).
Collivignarelli et al.71 described the application
of Fenton technology to the wastewaters of a
textile factory in substitution of the previously
used coagulationflocculation treatment, which did
not allow compliance with the discharge lim-
its.
Due to the complexity and high organic mat-
ter content of textile effluents several authors have
suggested the application of combined treatments
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment
including Fenton oxidation. Perez et al.93 investi-
gated the simultaneous use of Fenton, Fenton-like
and photo-Fenton for the treatment of textile wastew-
aters generated from a hydrogen peroxide bleaching
unit in Spain. The combination of these processes
was proved to be highly effective for the treatment
of this type of wastewaters. Lin and Peng94 stud-
ied the treatment of textile wastewaters from a large
dyeing and finishing mill by a continuous process
of combined coagulation, Fenton oxidation and acti-
vated sludge. An economic evaluation of the process
was carried out and the optimum operating condi-
tions were selected, the removal of COD reaching
almost 90% in those conditions. Fongsatitkul et al.95
investigated the potential of biological degradation
in association with Fenton oxidation for treating the
wastewaters from a textile factory in Central Thailand.
The authors compared the efficiency of different tech-
nologies: biological treatment in a sequencing batch
reactor (SBR) as a single process, Fenton oxidation
prior to that biological treatment and SBR followed
by Fenton oxidation. The best results were obtained
by the second arrangement, which attained more than
90% and close to 80% reduction of COD and colour,
respectively.
Food industry
The Fenton technology has also proved to be
effective for the treatment of wastewaters generated
by the food industry. This includes wastewaters from
olive oil extraction plants, commonly named olive
mill wastewaters96 98 and wastewaters generated
by the table olive producing industry.99 In the
former case, the oily juice is extracted from the
fruit through simple milling or, more recently,
by centrifugation. Table olive production requires
a previous treatment in order to eliminate the
bitterness of the fruit, due to the presence of
polyphenolic compounds. For this purpose, the olives
are treated with a 2% sodium hydroxide solution,
followed by consecutive water rinsings. The high
contaminant load of the wastewaters generated in
these processes includes polyphenols among the
most important pollutants. Moreover, the chelating
character of some compounds present in these
effluents leads to the presence of some toxic heavy
metals in solution. Anaerobic digestion has been
the most frequently used method for treating these
wastewaters. However, phenolic compounds inhibit
biological treatment to a great extent since phenols
are toxic to methanogenic bacteria at relatively low
concentrations.
Beltran de Heredia and Dom nguez99 applied
Fenton oxidation to the treatment of the liquor
resulting from black olive pickling, characterized by
high COD content (6700 mg L1 ) and the presence
of polyphenolic compounds. After 515 min reaction
time 73% of COD and 90% of polyphenols were
removed. The colour of these wastewaters was also
almost completely eliminated. Rivas et al.96 analyzed
1329
P Bautista et al.
the treatment of an olive oil mill wastewater (CODo =
12.8 g L1 ) from a southwestern Spain factory by
means of the Fenton technology. These authors
studied the influence of some operating variables
and proposed a kinetic model for the process. The
reaction between Fe3+ and H2 O2 was suggested to
be the controlling step. The simultaneous inefficient
decomposition of hydrogen peroxide into water
and oxygen was believed to play an important
role.
An integrated Fentoncoagulation/flocculation pro-
cess, using Ca(OH)2 , was applied by Beltran de
Heredia et al.100 to wine distillery wastewaters, com-
monly known as vinasses. The experimental variables
studied were H2 O2 and Fe doses, [H2 O2 ]o to [Fe2+ ]o
molar ratio, the effluent dilution and the way the
reagents were added (splitting the reagent doses into
different fractions). The optimal operating condi-
tions of the integrated process were established at
17 g L1 of H2 O2 and a [H2 O2 ]o to [Fe2+ ]o ini-
tial molar ratio of 15. The H2 O2 dose was below
one-half the stoichiometric amount relative to COD.
Under these conditions a COD removal of 74% was
attained.
Horng et al.101 evaluated the treatment of the
wastewater from a brewery plant containing high
COD and SS concentrations. The treatment included
biological (anaerobic and aerobic) processes and
Fenton oxidation. The resulting effluent satisfied the
existing local discharge standards. Fenton oxidation
was applied to simultaneously remove COD and SS
from the aerobic effluent so that a stable effluent
quality and increasingly stringent local discharge
limits in the future could be addressed. The
operating conditions were set at COD/H2 O2 = 1,
Fe2+ /H2 O2 = 2 (molar ratio), pH = 23 and 1 h
reaction time.
Gomec et al.102 reported on the improvement
of an existing treatment for olive mill wastew-
aters by including a Fenton oxidation step.
COD removal increased from 74 to almost
90%.
Cork processing industry
The main source of pollution in the cork processing
industry comes from the cork boiling step. After har-
vest from the producer tree, Quercus suber L., the cork
is stabilized by drying in open air for approximately
3 months. One of the first stages of industrial prepara-
tion of cork consists in its immersion for approximately
1 h in boiling water. This process improves cork
textural and plastic properties, making this mate-
rial more homogeneous, flat and elastic. The same
water may be repeatedly used up to 2030 times,
reaching temperatures of about 100 C during boiling,
with variable periods of cooling. The high volumes
of wastewaters produced (400 L t1 of cork) are
characterized by high COD, BOD and polyphenols
content, in the range of 4.55.5 g L1 , 1.11.8 g L1 of this integrated method is that small amounts of
1330
and 0.60.9 g L1 , respectively, as well as an acidic
pH, around 5.
Several authors have proposed different technical
solutions for cork processing wastewaters, involving
mainly physical-chemical methods. Guedes et al.103
used Fenton oxidation as a pre-treatment step in order
to improve biodegradability. The starting wastewater
had a high organic pollution (COD = 5000 mg L1 ,
TOC = 1505 mg L1 ) with a low biodegradability
(BOD5 /COD = 0.27). The authors accomplished a
kinetic study of the process and selected the opti-
mal operating conditions, achieving a COD reduction
of 87.3%. A rapid decrease of TOC was observed
within the initial 2 min, followed by a significantly
slower degradation. The oxidation proceeds through
an approximate second-order kinetics during the first
2 min of reaction, while the second phase of the
reaction can be described by a zero-order kinetic
equation.
Due to the complexity of these wastewaters, com-
bined techniques have frequently been suggested
to treat them. Peres et al.104 compared coagula-
tion/flocculation with Fenton oxidation followed by
coagulation/flocculation. The second arrangement
reduced COD, total polyphenols and aromatic com-
pounds by 74, 99 and 98%, respectively, representing
a considerable improvement compared with coagu-
lation/flocculation alone. Beltran de Heredia et al.105
also checked these two methods, reaching similar con-
clusions. From a kinetic study based on the initial
rate method they reported that the rate of COD
removal upon Fenton oxidation is maximum when
the H2 O2 /Fe2+ initial molar ratio is equal to 10.
In addition, these authors analyzed the effect of
the way of adding the reagents and observed that
the amount of organic matter (as COD) removed
by Fenton oxidation is increased by distributing
the H2 O2 and ferrous salt feeding in several addi-
tions.
Another combined process for the treatment of
cork boiling wastewater has been investigated by
Dias-Machado et al.106 These authors applied Fenton
oxidation as a pre-treatment, followed by biologi-
cal treatment. The use of this chemicalbiological
combined solution increases the bioavailability of the
polyphenols present in the wastewater since these com-
pounds are partially oxidized into simpler molecules,
improving their biodegradability. TOC reduction by
Fenton oxidation was very fast within the early stage
of the process (XTOC = 79% after 6 min), confirm-
ing the previous conclusion of Guedes et al.103 in the
sense that the first 35 min are sufficient to achieve
a high degree of chemical degradation. The results
obtained by Dias-Machado et al.106 showed that Fen-
ton oxidation, using small amounts of oxidant and
catalyst combined with a biodegradative inoculum,
added almost simultaneously, allows TOC reduc-
tions above 90%, a 20% better than the obtained
by chemical oxidation alone. The main advantage
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb

reagents are required for the Fenton oxidation, less
than half that previously recommended as optimal for
these wastewaters.
Landfill leachates
Although landfill leachates have been proved to be
toxic and recalcitrant, landfilling still remains one
of the main systems for municipal and industrial
solid waste disposal. The composition of landfill
leachates varies greatly depending on the type of
wastes and the age of the landfill. Biological treatments
including anaerobic and aerobic processes have shown
to be very effective in the early stages when dealing
with domestic wastes because the BOD/COD ratio
of the leachate has a high value. However, this
ratio generally decreases as the age of landfill
increases, due to the presence of pollutants that
inhibit biomass activity and/or are recalcitrant to
biological treatments. To treat these aged or refractory
landfill leachates different methods have been used,
such as flocculationprecipitation, adsorption on
activated carbon, evaporation, chemical oxidation and
incineration. Among them, growing interest has been
focused on advanced oxidation processes, which can
achieve a substantial reduction of COD and improve
the biodegradability.
Kang and Hwang107 studied the effectiveness
of Fenton oxidation against the non-biodegradable
organic substances present in a leachate from
Kimpo metropolitan landfill in Korea (CODo =
1500 mg L1 ). The overall COD removal efficiency
(by oxidation and coagulation) was maximum around
a pH of 3.5 in the oxidation step and drastically
decreased beyond pH = 5. Both the overall COD
removal efficiency and the efficiency by oxidation
itself were increased by increasing the H2 O2 dose.
Otherwise, a dose of ferrous sulphate beyond 500 mg
L1 did not increase the percentage of COD elimi-
nated.
Lopez et al.108 evaluated the application of the
Fenton process as pre-treatment for the leachate
from a municipal landfill located in southern
Italy (CODo = 10 540 mg L1 ) with the objective of
improving its overall biodegradability (BOD5 /COD
ratio) up to a level compatible with a biologi-
cal treatment (BOD5 /COD 0.5). The maximum
amount of COD that could be removed by the Fen-
ton pre-treatment was about 60%, using reagent
dosages of 10 000 mg L1 of H2 O2 and 830 mg
L1 of Fe2+ . The H2 O2 dose represented less than
one-half the stoichiometric amount with respect
to COD.
Primo et al.109 investigated the treatment of a
mature municipal landfill leachate from Cantabria
(Spain) in an integrated system pilot facility which
operated in batch and continuous mode. The sequence
of stages was: Fenton oxidation, neutralization of
Fenton effluent and ultrafiltration with submerged
membranes. The initial COD of the leachate averaged
2100 mg L1 and the BOD5 /COD ratio was 0.08.
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment
The final effluent was free of solids, colour and
Fe, and the COD reduction reached 80%. This
combination of Fenton with membrane filtration
showed highly efficient for the removal of recalcitrant
pollutants.
The Fenton-like process (Fe3+ -H2 O2 ) has also
shown to be an efficient treatment for the oxidation
of landfill leachate.110 It has been demonstrated that
the oxidation state of the catalyst does not affect to
the efficiency of the process in terms of COD removal.
Working temperatures above 30 C did not lead to
additional COD reduction and a less efficient use
of H2 O2 was observed. A rough economic analysis
of the process indicates that this treatment can be
a suitable alternative to deal with this type of liquid
wastes.
SUMMARY
Fenton oxidation has been demonstrated in full-
scale applications as a feasible technology for the
treatment of a wide diversity of industrial wastewaters.
It represents a useful solution in many cases where
the presence of recalcitrant and toxic pollutants
discards the use of conventional biological treatments.
Plant design and construction is simple and the
process does not imply any operating problem
other than controlling a safety handling of hydrogen
peroxide. In general it has low energy consumption
as it commonly works at ambient temperature and
pressure. The main economic drawback derives
from the consumption of oxidizing reagent (H2 O2 )
when dealing with high organic loads. Nevertheless,
this can be adapted to the case needs using this
technique as a conditioning treatment previous to
a biological process or in combination with some
other techniques, like coagulationflocculation or
membrane systems.
The cases described throughout the text are
collected in Table 1, which summarizes the state of
the art on the application of Fenton technology to
the treatment of industrial wastewaters. The economy
of this technology is very dependent on the H2 O2
consumption and in this respect the information
compiled from the literature reveals that a wide
range of H2 O2 to COD ratios have been used in
practice.
As indicated before, Fenton oxidation has been
used in connection with other techniques in integrated
wastewater treatments. Table 2 collects a representa-
tive list of examples.
ACKNOWLEDGEMENTS
The authors greatly appreciate financial support
from the Consejera de Educacion y Ciencia of
the CM through the project REMTAVARES (S-
0505/AMB/0395) and the Spanish MEC through
the project CONSOLIDER-TRAGUA (CSD2006-
0044).
1331
 1332
Table 1. Summary on the application of Fenton oxidation to industrial wastewaters
Industry Wastewater characteristics
1
Chemical Pesticides production: CODo = 235 mg L ;
organophosphorouso = 140158 g L1 ;
organochlorineo = 1657.5 g L1
Four types of industrial wastewater: CODo = 13 400,
2005, 1494 and 234 mg L1
Detergents production: CODo = 10 g L1
Petrochemical industry: TOCo = 94 mg L1
Cosmetic industry: CODo = 2395 and 4255 mg L1 ;
TOCo = 705 and 1090 mg L1 ;
BOD5o /CODo = 0.133 and 0.169
Phenolic resins manufacture: CODo = 2904 mg L1 ;
DOCo = 933 mg L1 ; phenolo = 1215 mg L1
Pigment production: CODo = 2700 mg L1 ;
BOD5o /CODo = 0.04; Colouro (454 nm) = 1.479 AU
Pharmaceutical CODo = 362 g L1 ; BOD5o /CODo = 0.008
Pulp and paper CODo = 1384 mg L1 ; TOCo = 441 mg L1
CODo = 1250 mg L1 ; TOCo = 537 mg L1 ;
Colouro (Pt) = 649 mg L1
CODo = 964 mg L1 ; BOD5o /CODo = 0.4; Total
solidso = 1396 mg L1 ;
Colouro (PtCo) = 4236 mg L1 ;
Odouro = 31 473 UO m3
DOI: 10.1002/jctb
J Chem Technol Biotechnol 83:13231338 (2008)
P Bautista et al.
Operating conditions Main results Ref
pH = 3.03.5; H2 O2 /COD = 21.2 (w/w); XCOD = 58.787.1%; Xorganophosphorous = 97100%; 69
H2 O2 /Fe2+ = 35 (molar); treaction = 2 h. Xorganochlorine > 90%
pH = 3.03.5; H2 O2 /COD = 0.37, 2.49, 2.68 and 21.37 XCOD = 71.788.6%; Xtoxicity (to Vibrio fischeri) = 70
(w/w); H2 O2 /Fe2+ = 35 (molar); treaction = 1.5 h. 1252%
Industrial scale. H2 O2 /COD = 0.25 (w/w); XCOD = 90% 71
H2 O2 /Fe2+ = 2 (molar).
T = 20 C; pH = 3.25; [H2 O2 ]o = 380 mg L1 ; XTOC = 65% 73
H2 O2 /Fe2+ = 3 (molar) treaction = 2 h.
T = 2550 C; pH = 3.0; H2 O2 /COD = 2.12 (w/w); XTOC = 4560%; XCOD = 69% 76
H2 O2 /Fe2+ = 4274 (molar); treaction = 4 h;
Vreaction = 50 mL.
Fenton or photo-Fenton (solar). Room temperature; Effective removal of phenol within 5 min. Fenton: 78
pH = 3; H2 O2 /COD = 2.2 (w/w); H2 O2 /Fe2+ = 38.5 XCOD = 82%; XDOC = 41%. Photo-Fenton:
(Fenton) and 77 (photo-Fenton) (molar); treaction = 2 h. XCOD = 97%; XDOC = 97%
T = 20.8 C; pH = 5; H2 O2 /COD = 1.85 (w/w); XCOD = 54.2%; BOD5 /COD = 0.36; Xcolour = 91.2% 79
H2 O2 /Fe2+ = 10 (molar). Batch: treaction = 0.5 h;
Vreaction = 500 mL.
T = 40 C; pH = 4; H2 O2 /COD = 0.28 (w/w); XCOD = 56.4% 80
H2 O2 /Fe2+ = 10 (molar); treaction = 1.5 h;
Vreaction = 100 mL.
Fenton or photo-Fenton. T = 25 and 70 C; pH = 2.8; Fenton: XTOC = 82%; Photo-Fenton: XTOC = 91% 85
H2 O2 /COD = 7.22 (w/w); H2 O2 /Fe2+ = 41 (molar);
treaction = 2 h; Vreaction = 100 mL; Solar or Xe light.
Fenton or photo-Fenton. T = 30 C; pH = 3; Fenton: XTOC = 90%; Photo-Fenton: XTOC = 93% 86
H2 O2 /COD = 5.76 (w/w); H2 O2 /Fe2+ = 26 (molar);
treaction = 15 min; Vreaction = 100 mL; Solar light
irradiation.
Fenton-like. Batch: room temperature; pH = 2.5; XCOD = 75%; Xcolour = 98%; Xaromatics = 95%; 88
H2 O2 /COD = 1.04 (w/w); H2 O2 /Fe3+ = 4 (molar); BOD5 /COD = 0.7; Treated wastewater toxic to
treaction = 1 h; Vreaction = 300 mL; Coagulation at Artemia salina
pH = 5.
 Table 1. Continued

Industry Wastewater characteristics Operating conditions Main results Ref

DOI: 10.1002/jctb
Pilot scale (continuous flow): tR = 1 h; Vreaction = 50 L (a Xodour = 96%; XVOCs (terpernes) = 80%
series of 2 reactors); Q = 100 L h1 .
Textile Four wastewaters: CODo = 3600, 1030, 1970 and T = 25 C; pH = 3.5; H2 O2 /COD = 0.194.7, XCOD = 60% (batch); XCOD = 30% (continuous flow). 89
3160 mg L1 0.6616.5, 0.358.63 and 0.225.38 (w/w); Significant colour reduction.
H2 O2 /(Fe2+ /Fe3+ ) = 125 (molar). Batch:
treaction = 2 h; Vreaction = 300 mL; Continuous flow:
tR = 1 h; Vreaction = 1 L.
Textile Combined industrial and domestic wastewater: Room temperature; pH = 3; H2 O2 /COD = 0.34 (w/w); XCOD = 95%; Xcolour = 100%; BOD5 /COD = 0.625 90
CODo = 1596 mg L1 ; BOD5o /CODo = 0.31; H2 O2 /Fe2+ = 2 (molar).
TSSo = 320 mg L1 ; oil and greaseo = 5.8 mg L1 ;

J Chem Technol Biotechnol 83:13231338 (2008)

heavy metalso = 18.32 mg L1
CODo = 910 mg L1 ; BOD5o /CODo = 0.16; T = 40 C; pH = 3.5; H2 O2 /COD = 0.88 (w/w); XCOD = 59%; Xcolour = 89%; Complete removal of the 91
Colouro (PtCo) = 1570 mg L1 H2 O2 /Fe2+ = 12 (molar). toxicity to Daphnia magna
CODo = 8100 mg L1 ; BOD5o /CODo = 0.148; Room temperature; pH = 3; H2 O2 /COD = 0.0037 (w/w); XCOD = 45%; XTOC = 40%; Xcolour = 71.5%; 92
TOCo = 3010 mg L1 H2 O2 /Fe2+ = 1.2 (molar). Batch: treaction = 46 h; BOD5 /COD = 0.097
Vreaction = 2 L.
CODo = 1669 mg L1 ; TOCo = 605 mg L1 ; Fenton or photo-Fenton. T = 70 C; pH = 3; Fenton: XTOC = 75%; Photo-Fenton: XTOC = 79% 93
Colouro (Pt) = 40 mg L1 H2 O2 /COD = 6 (w/w); H2 O2 /Fe2+ = 41 (molar);
treaction = 2 h; Vreaction = 100 mL; Xe light.
CODo = 1000 mg L1 T = 25 C; pH = 3; H2 O2 /COD = 0.5 (w/w); XCOD = 71% 39
[Fe2 O3 /carbon] = 300 mg L1 . Batch: treaction = 1 h;
Vreaction = 400 mL.
CODo = 800 mg L1 Industrial scale. H2 O2 /COD = 1.25 (w/w); XCOD = 55% 71
H2 O2 /Fe2+ = 1.2 (molar).
Food Olive oil mill wastewater: CODo = 12.8 g L1 T = 2050 C; pH = 2.8; H2 O2 /COD = 2.66 (w/w); XCOD = 6585% 96
H2 O2 /Fe2+ = 100 (molar); treaction = 8 h.
Food Olive oil mill wastewater: CODo = 167181 g L1 ; T = 25 C; pH = 4; H2 O2 /COD = 0.05 (w/w); XCOD = 56%; Xpolyphenols = 99.5%; Xcolour = 35%; 98
TSSo = 3639 g L1 ; Total polyphenolso = 5.2 g L1 ; H2 O2 /Fe2+ = 8.33 (molar); treaction = 4 h. Xaromatics = 33%
Turbidityo = 14.614.8 NTU
Table olive producing industry: CODo = 6700 mg L1 ; T = 30 C; pH = 4; H2 O2 /COD = 4 (w/w); XCOD = 73%; Xpolyphenols = 2690%; 99
BOD5o /CODo = 0.64; TSS = 5.2 g L1 ; Total H2 O2 /Fe2+ = 10 (molar); treaction = 1.5 h; Xaromatics = 3594%
polyphenolso = 0.12 g L1 ; Vreaction = 0.5 L.
Aromaticityo (254 nm) = 17.0 AU

1333
Fenton oxidation to industrial wastewaters treatment
 1334
Table 1. Continued
P Bautista et al.

Industry Wastewater characteristics Operating conditions Main results Ref

1
Cork processing CODo = 5000 mg L ; BOD5o /CODo = 0.27; T= 30 C; pH = 3.2; H2 O2 /COD = 2.12 (w/w); XCOD = 87.3%; XTOC = 66.4%; 103
TOCo = 1505 mg L1 H2 O2 /Fe2+ = 8.2 (molar); Vreaction = 200 mL. BOD5 /COD = 0.63
CODo = 3702 mg L1 ; BOD5o /CODo = 0.19; T = 30 C; pH = 3.5; H2 O2 /COD = 1.84 (w/w); XCOD = 65% 105
TSSo = 13901700 mg L1 ; Total H2 O2 /Fe2+ = 10 (molar); treaction = 2.5 h;
polyphenolso = 500620 mg L1 ; Vreaction = 0.5 L.
Aromaticityo (254 nm) = 0.961.17 AU (1/50 diluted
samples)
Landfill leachates CODo = 1500 mg L1 ; BOD5o /CODo = 0.02 T = 25 C; pH = 3.5; H2 O2 /COD = 1.1 (w/w); XCOD = 70% 107
H2 O2 /Fe2+ = 14.7 (molar); treaction = 3 h;
Vreaction = 1 L.
CODo = 10 540 mg L1 ; BOD5o /CODo = 0.22; Room temperature; pH = 3; H2 O2 /COD = 0.31 (w/w); XCOD = 25%; BOD5 /COD = 0.5 108
TOCo = 3900 mg L1 H2 O2 /Fe2+ = 19.7 (molar); treaction = 2 h.

Table 2. Application of Fenton oxidation in integrated wastewaters treatments

Industry Wastewater characteristics Operating conditions Main results Ref

Chemical Leather tannery industry: CODo = 319716797 mg L1 ;
BOD5o /CODo = 0.25
Pharmaceutical Three wastewater samples: CODo = 4000, 5400 and
13 130 mg L1 ; BOD7o /CODo = 0.33, 0.45 and
0.54 mg L1
CODo = 3540 g L1 ; BOD5o /CODo = 0.06
Textile CODo = 697 mg L1 ; Transparencyo = 3.7 cm
Combined Fenton and activated sludge system. XCOD 96% (Fenton: XCOD = 90%; Biological 74
H2 O2 /COD = 4 (w/w); H2 O2 /Fe2+ = 9 (molar). treatment: XCOD = 3560%; XBOD = 6070%)
Lab scale. Fenton-like + lime coagulation. Room XCOD = 8796%; XBOD7 = 7995% 82
temperature. H2 O2 /COD = 2 (w/w); H2 O2 /Fe2+ = 10
(molar); treaction = 2 h; Vreaction = 200 mL.
Industrial scale. Fenton + SBR (V = 8 m3 ; 24 h/cycle). XCOD = 98%; XBOD = 98%. Fenton unit: 83
Room temperature; pH = 3.5; XCOD = 4550%; BOD5 /COD = 0.23
H2 O2 /COD = 0.260.29 (w/w); H2 O2 /Fe2+ = 150
(molar); Vreaction = 2 m3 .
Continuous process of combined coagulation, Fenton XCOD = 88%; Transparency = 28.2 cm. 94
and activated sludge. pH = 4; H2 O2 /COD = 0.14
(w/w); H2 O2 /Fe2+ = 4.5 (molar);
[PAC]o = 100 mg L1 . Fenton: tR = 1 h;
Q = 1 mL min1 .

DOI: 10.1002/jctb
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb
Table 2. Continued

Industry Wastewater characteristics Operating conditions Main results Ref

CODo = 1047 mg L1 ; BOD5o /CODo = 0.42;
Colouro = 544 ADMI units
Comparison of SBR, Fenton + SBR and SBR + Fenton. Best option: Fenton + SBR : XCOD = 91%; 95
Lab.scale. Batch. Fenton: T = 2832 C; pH = 3; Xcolour = 80%
H2 O2 /COD = 0.0030.03 (w/w); H2 O2 /Fe2+ = 1
(molar); treaction = 0.5 h; Vreaction = 5 L. SBR: Three
reactors in parallel mode; T = 2832 C; V = 10 L;
24 h/cycle; STR = 60 days

J Chem Technol Biotechnol 83:13231338 (2008)

Food Wine distillery industry: CODo = 18.5 g L1 ; Integrated Fentoncoagulationflocculation process XCOD = 74% 100
TSSo = 13 g L1 (using Ca(OH)2 ). H2 O2 /COD = 0.92 (w/w);
H2 O2 /Fe2+ = 15 (molar).
Brewery industry: CODo = 16.3 g L1 Biological treatment (anaerobic and aerobic processes) Anaerobic process (UASB): XCOD = 90%; 101
and Fenton (pH = 23; H2 O2 /COD = 1 (w/w); Aerobic process: XCOD = 80%; Fenton:
H2 O2 /Fe2+ = 0.5 (molar); treaction = 1 h). XCOD = 35% and XSS = 40%
Cork processing CODo = 4250 mg L1 ; BOD5o /CODo = 0.19; Integrated Fentoncoagulation/flocculation process. XCOD = 74%; Xpolyphenols = 99%; 104
TSSo = 1720 mg L1 ; Total polyphenolso = 994 mg L1 ; T = 35 C; H2 O2 /COD = 4 (w/w); H2 O2 /Fe3+ = 81 Xaromatics = 98%; BOD5 /COD = 0.50
Aromaticityo (254 nm) = 2.16 AU (1/25 diluted samples) (molar); treaction = 5 h; Vreaction = 150 mL.
CODo = 23004600 mg L1 ; BOD5o /CODo = 0.150.21; Fenton oxidation + Biological treatment. T = 30 C; XTOC = 92% 106
TOCo = 12202000 mg L1 ; Total pH = 3.5; H2 O2 /COD = 1.092.17 (w/w);
polyphenolso = 660780 mg L1 H2 O2 /Fe2+ = 8.2 (molar); treaction = 0.5 h;
Vreaction = 1 L.
Landfill leachates CODo = 2100 mg L1 ; BOD5o /CODo = 0.08 Integrated system (Fenton + membrane filtration). Pilot XCOD = 80% (batch); XCOD = 83% (continuous); 109
plant. Room temperature; pH = 3; Batch: BOD5 /COD = 0.36
H2 O2 /COD = 4 (w/w); H2 O2 /Fe2+ = 13.8 (molar);
treaction = 1 h; Vreaction = 100 L. Continuous:
H2 O2 /COD = 3.3 (w/w); H2 O2 /Fe2+ = 11.4 (molar);
tresidence = 2 h.

1335
Fenton oxidation to industrial wastewaters treatment
P Bautista et al.
REFERENCES
1 Fenton HJH, Oxidation of tartaric acid in presence of iron. J
Chem Soc 65:899910 (1894).
2 Walling C, Fentons reagent revisited. Acc Chem Res
8:125131 (1975).
3 Al-Hayek N and Dore M, Oxidation of organic compounds
by Fentons reagent: possibilities and limits. Environ Technol
Lett 6:3750 (1985).
4 Pignatello JJ, Dark and photoassisted Fe3+ -catalyzed degra-
dation of chlorophenoxy herbicides by hydrogen peroxide.
Environ Sci Technol 26:944951 (1992).
5 Legrini O, Oliveros E and Braun AM, Photochemical pro-
cesses for water treatment. Chem Rev 93:671698 (1993).
6 Pignatello JJ, Oliveros E and MacKay A, Advanced oxidation
processes for organic contaminant destruction based on the
Fenton reaction and related chemistry. Crit Rev Env Sci
Technol 36:184 (2006).
7 Rahhal S and Richter HW, Reduction of hydrogen per-
oxide by the ferrous iron chelate of diethylenetriamine-
N,N,N ,N ,N -pentaacetate. J Am Chem Soc
110:31263133 (1988).
8 Bossmann SH, Oliveros E, Goeb S, Siegwart S, Dahlen EP,
Payawan L Jr, et al, New evidence against hydroxyl radicals
as reactive intermediates in the thermal and photochemically
enhanced Fenton reactions. J Phys Chem A102:55425550
(1998).
9 Pignatello JJ, Liu D and Huston P, Evidence for an additional
oxidant in the photoassisted Fenton reaction. Environ Sci
Technol 33:18321839 (1999).
10 Bachir S, Barbati S, Ambrosio M and Tordo P, Kinetics and
mechanism of wetair oxidation of nuclear-fuel-chelating
compounds. Ind Eng Chem Res 40:17981804 (2001).
11 Robert R, Barbati S, Ricq N and Ambrosio M, Intermediates
in wet oxidation of cellulose: identification of hydroxyl
radical and characterization of hydrogen peroxide. Water
Res 36:48214829 (2002).
12 Szpyrkowicz L, Juzzolino C and Kaul SN, A comparative
study on oxidation of disperse dyes by electrochemical
process, ozone, hypochlorite and Fenton reagent. Water
Res 35:21292136 (2001).
13 Bentez FJ, Acero JL, Real FJ, Rubio FJ and Leal AI, The
role of hydroxyl radicals for the decomposition of p-
hydroxy phenylacetic acid in aqueous solutions. Water Res
34:13381343 (2001).
14 Jones CW, Applications of Hydrogen Peroxide and Derivates. The
Royal Society of Chemistry, Cambridge, UK (1999).
15 Lucking F, Koser H, Jank M and Ritter A, Iron powder,
graphite and activated carbon as catalysts for the oxidation of
4-chlorophenol with hydrogen peroxide in aqueous solution.
Water Res 32:26072614 (1998).
16 Centi G, Perathoner S, Torre T and Verduna MG, Catalytic
wet oxidation with H2 O2 of carboxylic acids on homoge-
neous and heterogeneous Fenton-type catalysts. Cat Today
55:6169 (2000).
17 Centi G, Perathoner S and Romeo G, Fe/MFI as a new
heterogeneous Fenton-type catalyst in the treatment of
wastewater from agroindustrial processes. Studies in Surface
Science and Catalysis 135:51565163 (2001).
18 Fajerwerg K, Castan T, Foussard JN, Perrard A and Debelle-
fontaine H, Dependency on some operating parameters
during wet oxidation of phenol by hydrogen peroxide with
Fe-ZSM-5 zeolite. Environ Technol 21:337344 (2000).
19 He F, Shen XY and Lei LeC, Photochemically enhanced
degradation of phenol using heterogeneous Fenton-type
catalysts. J Environ SciChina 15:351355 (2003).
20 Melero JA, Calleja G, Martnez F, Molina R and Lazar K,
Crystallization mechanism of FeMFI from wetness
impregnated Fe2O3 SiO2 amorphous xerogels: Role of
iron species in Fenton-like processes. Micropor Mesopor Mat
74:1121 (2004).
21 Kuznetsova EV, Savinov EN, Vostrikova LA and Parmon VN,
Heterogeneous catalysis in the Fenton-type system
1336
FeZSM5/H2 O2 . Appl Catal B Environ 51:165170
(2004).
22 Kusic H, Koprivanac N and Selanec I, Fe-exchanged zeolite
as the effective heterogeneous Fenton-type catalyst for the
organic pollutant minimization: UV irradiation assistance.
Chemosphere 65:6573 (2006).
23 Makhotkina OA, Kuznetsova EV and Preis SV, Catalytic
detoxification of 1,1-dimethylhydrazine aqueous solutions
in heterogeneous Fenton system. Appl Catal B Environ
68:8591 (2006).
24 Barrault J, Abdellaoui M, Bouchoule C, Majeste A, Tati-
bouet JM, Louloudi A, et al, Catalytic wet peroxide oxi-
dation over mixed (AlFe) pillared clays. Appl Catal
B Environ 27:225230 (2000).
25 Catrinescu C, Teodosiu C, Macoveanu M, Miehe-Brendle J
and Le Dred R, Catalytic wet peroxide oxidation of
phenol over Fe-exchanged pillared beidellite. Water Res
37:11541160 (2003).
26 Guo J and Al-Dahhan M, Catalytic wet oxidation of phenol by
hydrogen peroxide over pillared clay catalyst. Ind Eng Chem
Res 42:24502460 (2003).
27 Carriazo J, Guelou E, Barrault J, Tatibouet JM, Molina R and
Moreno S, Catalytic wet peroxide oxidation of phenol by pil-
lared clays containing AlCeFe. Water Res 39:38913899
(2005).
28 Molina CB, Casas JA, Zazo JA and Rodrguez JJ, A compar-
ison of AlFe and ZrFe pillared clays for catalytic wet
peroxide oxidation. Chem Eng J 118:2935 (2006).
29 Al-Hayek N and Dore M, Oxidation of phenols in water by
hydrogen peroxide on alumina-supported iron. Water Res
24:973982 (1990).
30 Cuzzola A, Bernini M and Salvadori P, A preliminary study on
iron species as heterogeneous catalysts for the degradation
of linear alkylbenzene sulfonic acids by H2 O2 . Appl Catal
B Environ 36:231237 (2002).
31 Melero JA, Calleja G, Martnez F, Molina R and Pariente MI,
Nanocomposite Fe2 O3 /SBA15: an efficient and stable
catalyst for the catalytic wet peroxidation of phenolic
aqueous solutions. Chem Eng J 131:245256 (2007).
32 Martnez F, Melero JA, Botas JA, Pariente MI and Molina R,
Treatment of phenolic effluents by catalytic wet hydrogen
peroxide oxidation over Fe2 O3 /SBA15 extruded catalyst
in a fixed-bed reactor. Ind Eng Chem Res 46:43964405
(2007).
33 Parvulescu V and Su BL, Iron, cobalt or nickel substituted
MCM-41 molecular sieves for oxidation of hydrocarbons.
Cat Today 69:315322 (2001).
34 Hu X, Lam FLY, Cheung LM, Chan KF, Zhao XS and
Lu GQ, Copper/MCM-41 as catalyst for photochemically
enhanced oxidation of phenol by hydrogen peroxide. Cat
Today 68:129133 (2001).
35 Oliveira LCA, Goncalves M, Guerreiro MC, Ramalho TC,
Fabris JD, Pereira MC et al, A new catalyst material
based on niobia/iron oxide composite on the oxidation of
organic contaminants in water via heterogeneous Fenton
mechanisms. Appl Catal AGen 316:117124 (2007).
36 Moura FCC, Araujo MH, Costa RCC, Fabris JD, Ardis-
son JD, Macedo WAA et al, Efficient use of Fe metal
as an electron transfer agent in a heterogeneous Fen-
ton system based on Fe0 /Fe3 O4 composites. Chemosphere
60:11181123 (2005).
37 Costa RCC, Lelis MFF, Oliveira LCA, Fabris JD, Ardis-
son JD, Rios RRVA, et al, Novel active heterogeneous Fen-
ton system based on Fe3 x Mx O4 (Fe, Co, Mn, Ni): The
role of M2+ species on the reactivity towards H2 O2 reactions.
J Hazard Mater 129:171178 (2006).
38 Liou RM, Chen SH, Hung MY, Hsu CS and Lai JY, Fe(III)
supported on resin as effective catalyst for the heterogeneous
oxidation of phenol in aqueous solution. Chemosphere
59:117125 (2005).
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb

39 Dantas TLP, Mendonca VP, Jose HJ, Rodrigues AE and Mor-
eira RFPM, Treatment of textile wastewater by heteroge-
neous Fenton process using a new composite Fe2 O3 /carbon.
Chem Eng J 118:7782 (2006).
40 Zazo JA, Casas JA, Mohedano AF and Rodrguez JJ, Catalytic
wet peroxide oxidation of phenol with a Fe/active carbon
catalyst. Appl Catal BEnviron 65:261268 (2006).
41 Eisenhauer HR, Oxidation of phenolic wastes. J Water Poll
Control Fed 36:11161128 (1964).
42 Beltran de Heredia J, Torregrosa J, Domnguez JR and
Peres JA, Kinetic model for phenolic compound oxidation
by Fentons reagent. Chemosphere 45:8590 (2001).
43 Kang N, Lee DS and Yoon J, Kinetic modeling of Fenton
oxidation of phenol and monochlorophenols. Chemosphere
47:915924 (2002).
44 Zazo JA, Casas JA, Mohedano AF, Gilarranz MA and
Rodrguez JJ, Chemical pathway and kinetics of phe-
nol oxidation by Fentons reagent. Environ Sci Technol
39:92959302 (2005).
45 Barbeni M, Minero C, Pelizzetti E, Borgarello E and Ser-
pone N, Chemical degradation of chlorophenols with Fen-
tons reagent. Chemosphere 16:22252237 (1987).
46 Potter FJ and Roth JA, Oxidation of chlorinated phenols using
Fentons reagent. Hazard Waste Hazard Mater 10:151170
(1993).
47 Kwon BG, Lee DS, Kang N and Yoon J, Characteristics of
p-chlorophenol oxidation by Fentons reagent. Water Res
33:21102118 (1999).
48 Basu S and Wei IW, Mechanism and kinetics of oxidation of
2,4,6-trichlorophenol by Fentons reagent. Environ Eng Sci
17:279290 (2000).
49 Murphy AP, Boegli WJ, Price MK and Moody CD, A Fenton-
like reaction to neutralize formaldehyde waste solutions.
Environ Sci Technol 23:166169 (1989).
50 Kang SF, Wang TH and Lin YH, Decolorization and degrada-
tion of 2,4-dinitrophenol by Fentons reagent. J Environ Sci
Health Part A Toxic/Hazard Subst Environ Eng 34:935950
(1999).
51 Wang TH, Kang SF and Lin YH, Comparison among Fenton-
related processes to remove 2,4-dinitrophenol. J Environ
Sci Health Part A Toxic/Hazard Subst Environ Eng
34:12671281 (1999).
52 Li ZM, Shea PJ and Comfort SD, Fenton oxidation of 2,4,6-
trinitrotoluene in contaminated soil slurries. Environ Eng Sci
14:5566 (1997).
53 Li ZM, Peterson MM, Comfort SD, Horst GL, Shea PJ and
Oh BT, Remediating TNT-contaminated soil by soil wash-
ing and Fenton oxidation. Sci Total Environ 204:107115
(1997).
54 Mohanty NR and Wei IW, Oxidation of 2,4-dinitrotoluene
using Fentons reagent: reaction mechanisms and their prac-
tical applications. Hazard Waste Hazard Mater 10:171183
(1993).
55 Sedlak DL and Andren AW, Oxidation of chlorobenzene with
Fentons reagent. Environ Sci Technol 25:777782 (1991).
56 Watts RJ, Jones AP, Chen PH and Kenny A, Mineral-
catalyzed Fenton-like oxidation of sorbed chlorobenzenes.
Water Environ Res 69:269275 (1997).
57 Yoshida M, Lee BD and Hosomi M, Decomposition of
aqueous tetrachloroethylene by Fenton oxidation treatment.
Water Sci Technol 42:203208 (2000).
58 Tang WZ and Tassos S, Oxidation kinetics and mecha-
nisms of trihalomethanes by Fentons reagent. Water Res
31:11171125 (1997).
59 Casero I, Sicilia D, Rubio S and Perez-Bendito D, Chemical
degradation of aromatic amines by Fentons reagent. Water
Res 31:19851995 (1997).
60 Hundal LS, Singh J, Bier EL, Shea PJ, Comfort SD and
Powers WL, Removal of TNT and RDX from water and
soil using iron metal. Environ Pollut 97:5564 (1997).
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment
61 Zoh KD and Stenstrom MK, Fenton oxidation of hexahydro-
1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-
tetranitro-1,3,5,7-tetrazocine (HMX). Water Res
36:13311341 (2002).
62 Bigda RJ, Consider Fentons chemistry for wastewater treat-
ment. Chem Eng Prog 91:6266 (1995).
63 Tyre BW, Watts RJ and Miller GC, Treatment of four
biorefractory contaminants in soils using catalyzed hydrogen
peroxide. J Environ Qual 20:832838 (1991).
64 Ravikumar JX and Gurol MD, Fentons reagent as a chemical
oxidant for soil contaminants. Chem Oxid 2:206229 (1992).
65 Ravikumar JX and Gurol MD, Chemical oxidation of chlori-
nated organics by hydrogen peroxide in the presence of sand.
Environ Sci Technol 28:394400 (1994).
66 Kong SH, Watts RJ and Choi JH, Treatment of petroleum-
contaminated soils using ironmineralcatalyzed hydrogen
peroxide. Chemosphere 37:14731482 (1998).
67 Watts RJ, Udell MD, Kong S and Leung SW, Fenton-like soil
remediation catalyzed by naturally occurring iron minerals.
Environ Eng Sci 16:93103 (1999).
68 Kanmani S and Muthuselvi S, Soil remediation by Fen-
ton/photoFenton oxidation processes. Journal of the Insti-
tution of Public Health Engineers 2:59 (2005).
69 Barbusinski K and Filipek K, Use of Fentons reagent for
removal of pesticides from industrial wastewater. Pol J
Environ Stud 10:207212 (2001).
70 Barbusinski K, Toxicity of industrial wastewater treated by
Fentons reagent. Pol J Environ Stud 14:1116 (2005).
71 Collivignarelli C, Riganti V, Teruggi S and Montemagno F,
Treatment of industrial wastewater with Fentons reagent.
Part II. Ingegneria Ambientale 26:409418 (1997).
72 Lopez R, Nunez O, Morales F, Calderon C and Liewald W,
Application of advanced oxidant systems in the treatment of
residual waters in the petroleum industry (Fenton system).
Acta cientfica venezolana 50:7580 (1999).
73 Gao Y, Yang M, Hu J and Zhang Y, Fentons process for
simultaneous removal of TOC and Fe2+ from acidic waste
liquor. Desalination 160:123130 (2004).
74 Vidal G, Nieto J, Mansilla HD and Bornhardt C, Combined
oxidative and biological treatment of separated streams of
tannery wastewater. Water Sci Technol 49:287292 (2004).
75 Dantas TLP, Jose HJ and Moreira RFPM, Fenton and photo-
Fenton oxidation of tannery wastewater. Acta Scientiarum,
Technology 25:9195 (2003).
76 Bautista P, Mohedano AF, Gilarranz MA, Casas JA and
Rodrguez JJ, Application of Fenton oxidation to cosmetic
wastewaters treatment. J Hazard Mater 143:128134
(2007).
77 Coste M, Batbedat C, Feliers C, Olejnik D, Cigana J and Cer-
vantes P, Refractory COD removal in the chemical industry:
technico-economic comparison of advanced oxidation pro-
cesses, in Proceedings of WEFTEC03, 76th Annual Technical
Exhibition & Conference, Los Angeles, CA, 1115 October
(2003).
78 Kavitha V and Palanivelu K, The role of ferrous ion in Fenton
and photo-Fenton processes for the degradation of phenol.
Chemosphere 55:12351243 (2004).
79 Park TJ, Lee KH, Jung EJ and Kim CW, Removal of refractory
organics and color in pigment wastewater with Fenton
oxidation. Water Sci Technol 39:189192 (1999).
80 San Sebastian N, Fguls J, Font X and Sanchez A, Pre-
oxidation of an extremely polluted industrial wastewater
by the Fentons reagent. J Hazard Mater B101:315322
(2003).
81 Hofl C, Sigl G, Specht O, Wurdack I and Wabner D, Oxida-
tive degradation of AOX and COD by different advanced
oxidation processes. A comparative study with two sam-
ples of a pharmaceutical wastewater. Water Sci Technol
35:257264 (1997).
82 Kulik N, Trapido M, Goi A, Veressinina Y and Munter R,
Combined chemical treatment of pharmaceutical efflu-
ents from medical ointment production. Chemosphere
70:15251531 (2008).
1337
P Bautista et al.
83 Tekin H, Bilkay O, Ataberk SS, Balta TH, Ceribasi IH,
Sanin FD, et al, Use of Fenton oxidation to improve the
biodegradability of a pharmaceutical wastewater. J Hazard
Mater 136:258265 (2006).
84 Thompson G, Swain J, Kay M and Forster CF, The treatment
of pulp and paper mill effluent: a review. Bioresource Technol
77:275286 (2001).
85 Perez M, Torrades F, GarcaHortal JA, Domenech X and 99
Peral J, Removal of organic contaminants in paper pulp
treatment effluents under Fenton and photo-Fenton condi-
tions. Appl Catal B Environ 36:6374 (2002).
86 Torrades F, Perez M, Mansilla HD and Peral J, Experimental
design of Fenton and photo-Fenton reactions for the
treatment of cellulose bleaching effluents. Chemosphere
53:12111220 (2003).
87 Pera-Titus M, Garca-Molina V, Banos MA, Gimenez J and 101
Esplugas S, Degradation of chlorophenols by means of
advanced oxidation processes: a general review. Appl Catal
B Environ 47:219256 (2004).
88 Tambosi JL, Di Domenico M, Schirmer WN, Jose HJ and
Moreira RFPM, Treatment of paper and pulp wastewater
and removal of odorous compounds by a Fenton-like process
at the pilot scale. J Chem Technol Biotechnol 81:14261432
(2006).
89 Flaherty KA Jr and Huang CP, Batch and continuous flow
applications of Fentons reagent and Fenton-like chemistry
for the treatment of refractory textile wastewaters. Chem
Oxid 3:112133 (1994).
90 Badawy MI and Ali MEM, Fentons peroxidation and coagu-
lation processes for the treatment of combined industrial and
domestic wastewater. J Hazard Mater 136:961966 (2006).
91 Meric S, Selcuk H and Belgiorno V, Acute toxicity removal
in textile finishing wastewater by Fentons oxidation,
ozone and coagulationflocculation processes. Water Res
39:11471153 (2005).
92 Papadopoulos AE, Fatta D and Loizidou M, Development and
optimization of dark Fenton oxidation for the treatment of
textile wastewaters with high organic load. J Hazard Mater
146:558563 (2007).
93 Perez M, Torrades F, Domenech X and Peral J, Fenton and
photo-Fenton oxidation of textile effluents. Water Res
36:27032710 (2002).
94 Lin SH and Peng CF, A continuous Fentons process for
treatment of textile wastewater. Environ Technol 16:693699
(1995).
95 Fongsatitkul P, Elefsiniotis P, Yamasmit A and Yamasmit N,
Use of sequencing batch reactors and Fentons reagent to
treat a wastewater from a textile industry. Biochem Eng J
21:213220 (2004).
96 Rivas FJ, Beltran FJ, Gimeno O and Frades J, Treatment of
olive oil mill wastewater by Fentons reagent. J Agric Food
Chem 49:18731880 (2001).
97 Nasr B, Ahmed B and Abdellatif G, Fenton treatment of
olive oil mill wastewater. Applicability of the method and
1338
parameters effects on the degradation process. J Environ
Sci China 16:942944 (2004).
98 Ahmadi M, Vahabzadeh F, Bonakdarpour B, Mofarrah E and
Mehranian M, Application of the central composite design
and response surface methodology to the advanced
treatment of olive oil processing wastewater using Fentons
peroxidation. J Hazard Mater 123:187195 (2005).
Beltran de Heredia J and Domnguez JR, Aplicacion del
reactivo Fenton para la depuracion de las aguas residuales
de la industria productora de aceituna de mesa. Tecnologa
del Agua 21:5058 (2001).
100 Beltran de Heredia J, Domnguez JR and Partido E, Physico-
chemical treatment for the depuration of wine distillery
wastewaters (vinasses). Water Sci Technol 51:159166
(2005).
Horng RY, Perng MJ, Tzou WY, Chen CH, Wu HS, Shao H,
et al, A case study of a brewery factory wastewater treatment
by anaerobic/aerobic and Fenton process, in Proceedings of
WEFTEC96, 69th Annual Conference & Exposition, Dallas,
TX, 59 October, Vol. 3, pp. 531538 (1996).
102 Gomec CY, Erdim E, Turan I, Aydin AF and Ozturk I,
Advanced oxidation treatment of physico-chemically pre-
treated olive mill industry effluent. J Environ Sci Health Part
B Pestic Contam Agric Wastes 42:741747 (2007).
103 Guedes AMFM, Madeira LMP, Boaventura RAR and Costa
CAV, Fenton oxidation of cork cooking wastewater overall
kinetic analysis. Water Res 37:30613069 (2003).
104 Peres JA, Beltran de Heredia J and Domnguez JR, Integrated
Fentons reagentcoagulation/flocculation process for the
treatment of cork processing wastewaters. J Hazard Mater
B107:115121 (2004).
105 Beltran de Heredia J, Domnguez JR and Lopez R, Advanced
oxidation of cork-processing wastewater using Fentons
reagent: kinetics and stoichiometry. J Chem Technol
Biotechnol 79:407412 (2004).
106 Dias-Machado M, Madeira LM, Nogales B, Nunes OC and
Manaia CM, Treatment of cork boiling wastewater
using chemical oxidation and biodegradation. Chemosphere
64:455446 (2006).
107 Kang YW and Hwang KY, Effects of reaction conditions on
the oxidation efficiency in the Fenton process. Water Res
34:27862790 (2000).
108 Lopez A, Pagano M, Volpe A and Di Pinto AC, Fentons
pre-treatment of mature landfill leachate. Chemosphere
54:10051010 (2004).
109 Primo O, Rueda A, Rivero MJ and Ortiz I, An integrated
process, Fenton reactionultrafiltration, for the treatment
of landfill leachate: pilot plant operation and analysis. Ind
Eng Chem Res 47:946952 (2008).
110 Rivas FJ, Beltran F, Gimeno O and Carvalho F, Fenton-like
oxidation of landfill leachate. J Environ Sci Health Part
A Toxic/Hazard Subst Environ Eng 38:371379 (2003).
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb