498 Ind. Eng. Chem. Res.

2010, 49, 498–505

Heterogeneous Fenton Catalyst Supports Screening for Mono Azo Dye

Degradation in Contaminated Wastewaters
A. Rodrı́guez,* G. Ovejero, J. L. Sotelo, M. Mestanza, and J. Garcı́a*
Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingenierı́a Quı́mica, Facultad de
Ciencias Quı́micas, UniVersidad Complutense de Madrid, AVda. Complutense s/n, 28040 Madrid, Spain

Degradation of acid orange II (AOII), a dye present in textile industry wastewater, by the heterogeneous
Fenton process (HFP) was performed. In order to select an adequate support, heterogeneous Fenton catalysts
were prepared using several materials such as carbon nanotubes, carbon nanofibers, activated carbon,
hydrotalcite-like materials, mesoporous silica (MCM41), silica, silica xerogel, sepiolite, and zeolite USY,
that were tested in the degradation of AOII as the model compound. Color, total organic carbon, chemical
oxygen demand removal, and toxicity were studied in the process. The best catalyst was iron supported on
sepiolite. The best performing catalytic material was used to investigate the influence of the presence of
carbonate ions, pH, and reuse of catalyst. Also, a real textile wastewater was successfully treated with this
catalyst.

1. Introduction
There is a wide variety of dyes on the market for various
applications. Dyes can be classified as azo dyes, triaryl methane
dyes, anthraquinone dyes, heterocyclic dyes, and phthalocyanine
dyes, depending on their chemical structures. Dyes can also
be characterized according to their application method as
reactive dyes, direct dyes, acidic dyes, disperse dyes, and
cationic dyes.
Effluents from the textile industry commonly contain high
concentration of organic and inorganic chemicals and are
characterized by very high chemical oxygen demand (COD)
and total organic corbon (TOC) values as well as strong color.1
Physical, chemical, and biological methods are available for
treatment of wastewater discharged from these industries.
However, physical methods, such as liquid-liquid extraction,
ion-exchange, adsorption, air or steam stripping, etc., are
ineffective on pollutants which are not readily adsorbable or
volatile and have further disadvantages because they simply
transfer the pollutants to another phase rather than destroying
them.
In recent years, advanced oxidation processes (AOPs) have
been intensively investigated.2 Homogeneous Fenton reaction
is already in use for industrial wastewater purification processes.3
Several studies have been published concerning supporting
Fenton’s catalyst to various carriers, such as brick grain, MgO,
SiO2, and zeolite.4 Also copper or iron containing pillared clays
were used as Fenton’s catalysts.5 Some recent reviews on the
use of Fenton reagents have been published.6,7
It is well-known that, in theory, the most important charac-
teristics of heterogeneous Fenton processes is the formation of
OH radicals, which are highly oxidative, nonselective, and able
to decompose many organic compounds. It is also well-accepted
that the advantages of heterogeneous Fenton processes are
complete mineralization of organic compounds at ambient
temperature and easy separation of the heterogeneous catalysts
from the treated wastewater. Because of these advantages, a
lot of effort has been made in developing heterogeneous Fenton
catalysts containing Fe ions.
* To whom correspondence should be addressed. Tel.: +34-91-394-
4182. Fax: +34-91-394-4114. E-mail address: arodri@quim.ucm.es
(A.R.); juangcia@quim.ucm.es (J.G.).
10.1021/ie901212m CCC: $40.75  2010 American Chemical Society
Published on Web 10/29/2009
The Fenton system uses ferrous ions as catalysts that react
with hydrogen peroxide, producing hydroxyl radicals with
powerful oxidizing abilities:
H2O2 + Fe2+ f HO• + HO- + Fe3+ (1)
Generated hydroxyl radicals may then react with ferrous ions,
for instance, to form ferric ions, or with the organics:
Fe2+ + HO• f HO- + Fe3+ (2)
HO• + organics f products (3)
The oxidation products are usually low molecular weight
compounds that are often more easily biodegradable or, in some
instances, the organic compounds reduced to carbon dioxide
and water, among other inorganics.
In our previous work, we have investigated catalytic activity
and selectivity of several catalysts, Pt, Cu, Ru, Pd, Re, and Fe
supported on commercial and synthesized multiwalled carbon
nanotubes, carbon nanofibers, activated carbon, SBA15, etc.,
in several processes such as catalytic wet air oxidation and
catalytic wet peroxide oxidation.1,8-10 This work is primarily
focused on utilization of catalysts in removal of aromatic
compounds.
In the present work, we have compared and discussed the
catalytic activity of iron catalysts prepared over different
supports in the heterogeneous Fenton process (FHP) of acid
orange II (AOII) as the model compound. Acid orange II was
selected as the model compound to represent the concerned dye
group, because it is inexpensive and frequently used in the
textile, pulp, and paper industries.
2. Materials and Methods
2.1. Dye. The azo dye, acid orange II (color index number
15510), was kindly supplied by Sigma Aldrich (Spain) as
commercially available dye and used without further purifica-
tion. Table 1 shows the main characteristics and structure of
this dye. The hydrogen peroxide (30%), FeSO4 · 7H2O, and all
other chemicals were obtained from Merck, Germany. The
textile wastewater sample was provided by the dyeing process
of Textil Navazo Factory, Béjar, Spain.
 Ind. Eng. Chem. Res., Vol. 49, No. 2, 2010 499
Table 1. Main Characteristics and Structure of AOII

Table 2. Nomenclature of Iron Catalysts and Textural Properties 2.4. Catalytic Activity. Chemical oxidation of acid orange
catalyst nomenclature SBET (m2 · g-1) APS (Å)a II (Fluka p.a.) was carried out using 0.25 L of reaction, T ) 30
°C, catalyst load ) 0.5 g (5% Fe), H2O2/AOII ) 5 w/w, H2O2/
hydrotalcite Fe-HT 69.7 153.5
zeolite USY Fe-USY 172.9 19.0 Fe2+ ) 3.5 w/w, pH ) 3.0, and reaction time of 120 min, in a
AC Fe-AC 673.9 24.3 jacketed glass batch reactor.13 Briefly, the reactor is provided
silica Fe-S 392.7 17.7 with a magnetic stirrer and a thermostatic bath. After stabiliza-
MCM41 Fe-MCM 857.4 23.2 tion of temperature and pH, the powder catalyst was added
silica xerogel Fe-X 500.6 18.5
followed by the H2O2 solution (30% w/w, from Merck), this
CNT Fe-CNT 106.5 169.9
CNF Fe-CNF 141.1 158.2 being considered the initial instant of reaction (t ) 0);
sepiolite Fe-SEP 201.9 85.2 absorbance, temperature, and pH were then permanently mea-
a
Average pore size.
sured. In particular, the azo dye in the reaction was quantified
through measurement of the absorbance at maximum wave-
2.2. Preparation of the Catalysts. Nine different supports length (λmax ) 486 nm) of AOII followed by concentration
(carbon nanotubes (CNT), carbon nanofibers (CNF), active calculation according to predetermined calibration curve. A
carbon (AC), hydrotalcite (HT), mesoporous silica (MCM41), UV-vis spectrophotometer (Shimadzu spectrophotometer model
silica (S), silica xerogel (SX), sepiolite (SEP), and zeolite USY UV-2401-PC) was used to analyze the samples. The pH or the
(USY)) were used as Fe-catalysts. The HT, MCM41, CNT, and solution was kept almost unchangeable, due to the low
SX were synthesized in our laboratories, whereas USY, AC, S, concentration of the AOII solution used. Replicas of some of
the experiments allowed the conclution that, for each run,
CNF, and SEP were commercial. The HT was prepared using
experimental data do not differ, on average, more than 5%.
the decomposing property of urea at high temperature.11 The
2.5. Analytical Methods. To evaluate the mineralization of
MCM4112 was synthesized by hydrothermal method. The carbon
the dye, total organic carbon (TOC) was measured using a
nanotubes were synthesized by thermal chemical vapor deposi-
Rosemount-Dohrmann DC-190 TOC analyzer. Reported TOC
tion (CVD). Carbon nanotubes were grown on Fe metal
values represent the average of three measurements at least.
deposited in a flowing gas mixture of acetylene and nitrogen.
Chemical oxygen demand was measured on a PF11 photometer
The material was then purified by a sulphuric acid treatment,
Macherey-Nagel according to standard methods.14 The total Fe
aiming at the total dissolution of alumina and partial elimination
in the solution was determined using the phenanthroline
of iron contained in the tubes. The final material has a purity
method.14 The toxicity and presence of some organic compounds
of 97%. The surface chemistry of the carbon nanotubes was
in wastewater were determined by means of a Microtox analyzer
modified by introducing carboxylic acid (-COOH) groups by
model 500 and a GC-MS chromatograph (Agilent 5973 N
means of an acidic treatment (HNO3, 5 M) for 3 h under reflux.
MSD), respectively. Also, the wastewater were analyzed ac-
Then, the support was washed with water and dried overnight
cording to standard methods described elsewhere,14 shown are
at 110 °C. Finally, the silica xerogel preparation started from
the following average values for the main parameters: pH )
TEOS solution hydrolysis with drops of hydrochloric acid. After
8.7 ( 0.2; the organic matter content measured as TOC ) 5.9
24 h, hexamethylenetetramine aqueous (35.8 wt %, 10 mL)
( 0.1 g · L-1 and COD ) 17.9 ( 0.1 g · L-1; BOD5 ) 5.5 (
solution was added to accelerate the gelation and the gel was
0.1 g · L-1; TSS ) 23.9 ( 0.05 g · L-1; TDS ) 12.0 ( 0.05
dried at 110 °C for 12 h to obtain a xerogel.
g · L-1; the ecotoxicity measured like EC50 after 15 min of
The mass of precursor was calculated in order to obtain 5 wt exposition was 2.8%.
% iron in the catalysts. After incipient wetness impregnation,
the wet solid was dried overnight at 110 °C and then activated 3. Results and Discussion
under N2 (carbonaceous materials) flowing at 350 °C for 4 h in
a furnace and 550 °C in the other materials. 3.1. Support and Catalyst Characterizations. The nine
2.3. Catalyst Characterization. Textural characterization heterogeneous catalysts containing Fe were first characterized
was carried out by N2 adsorption at 77 K. The BET surface by N2 adsorption-desorption at 77 K. Some of these isotherms
areas (SBET) were calculated from the corresponding nitrogen are shown in Figure 1. According to IUPAC, hydrotalcite,
adsorption isotherms. The morphology of the supports and carbon nanotubes, carbon nanofibers, activated carbon and
catalysts was analyzed by scanning electron microscopy (SEM). sepiolite show a type IV N2 isotherm, characteristic of meso-
Experiments were carried out with a Jeol JSM 6400 electron porous materials. Zeolite USY, silica, and silica xerogel have
microscopy at 22 keV. X-ray diffraction (XRD) was recorded type I N2 isotherms, characteristic of microporous materials.
by means of a difractometer Siemens D-501 with a Ni-filtered The morphology of the catalysts was analyzed by TEM. Their
Cu KR radiation in order to check some structure data. Finally, structures, which are defined by those of the corresponding
X-ray fluorescence (XRF) measurements were performed using supports, are shown in Figure 2 for sepiolite (raw and after
a Bruker S4 Explorer system, with software for data acquisition reaction) and carbon nanotubes, as examples of carbonaceous
and analysis. Table 2 shows the nomenclature of catalysts and and not carbonaceous materials. The sepiolite structure (Figure
the textural properties. 2a) is composed by heterogeneous appearance with large pores.
500 Ind. Eng. Chem. Res., Vol. 49, No. 2, 2010

Figure 1. Adsorption/desorption isotherms of N2 in several catalysts studied in FHP.

Figure 2. SEM images of (a) sepiolite, (b,c) sepiolite after reaction, and (d) carbon nanotubes.

Energy dispersive X-ray (EDX) analysis allows the identification

of deposits of iron oxide as well as AOII molecules adsorbed
after reaction (Figure 2b and c). The carbon nanotubes (Figure
2d) exist as nearly endless, highly tangled ropes.
X-ray analysis of Fe-CNT (raw and after reaction) and
sepiolite are shown in Figure 3. Characteristics peaks, (002)
and (100), of the graphite structure are visible,15 corresponding
to the periodicity between the graphene layers and within the
graphene layer respectively. The characteristic XRD peak of
iron (2θ ) 45.3) was visible clearly. After reaction, the Fe-
CNT shows new peaks. These peaks correspond to distortion
of catalyst surface by the strong dye adsorption.16
3.2. Heterogeneous Fenton Process. 3.2.1. Degradation
of AOII. An experiment was carried out to evaluate the ability
of H2O2 to eliminate AOII in aqueous solutions without the Figure 3. XRD of carbon nanotubes and sepiolite (raw and after
addition of any heterogeneous Fenton catalyst. The results shown heterogeneous Fenton reaction).
that AOII degradation due to hydrogen peroxide is almost to its low oxidation potential as compared to hydroxyl or
negligible (<1.0% after 2 h, blank), which might be attributed perhydroxyl radicals.17
 Ind. Eng. Chem. Res., Vol. 49, No. 2, 2010 501

Figure 4. Reduction of color by several iron supported catalysts.

Figure 5. Evolution of AOII concentration by several iron supported catalysts.

From the spectrum’s analysis of the absorption peaks, the Table 3. Rate Constants of Several Iron Catalysts in FHR of AOII
Solution
decay of dye color in terms of absorbance is shown in Figure
4. Also, in Figure 5, we can see the evolution of conversion catalyst kHFR R2
versus time. A fast conversion of AOII was observed in all Fe-HT 0.0108 0.8823
samples. A complete AOII conversion is reached in 45 min or Fe-USY 0.0120 0.9917
less, for Fe-SEP and Fe-AC but not in the case of Fe-USY, Fe-AC 0.1228 0.9554
Fe-SX, and Fe-MCM41 catalysts. For a reaction time of 120 Fe-S 0.0717 0.9935
Fe-MCM 0.0068 0.9871
min, the highest efficiency in all parameters was obtained with Fe-X 0.0131 0.9601
Fe-SEP catalyst. MCM41 was the least effective support of the Fe-CNT 0.0046 0.9726
nine tested materials. Fe-CNF 0.0358 0.8749
In general, the Fenton reaction rates on the degradation of Fe-SEP 0.0620 0.9963
organic pollution have been described well by the apparent
pseudo-first-order equation:17 Having in mind the adsorption contribution for carbon-based
materials, the kinetic constants in Table 3 have not the physical
-ln ()
Ct
C0
) kHFRt (4)
meaning of a first order chemical reaction kinetics. In this sense,
it is necessary to check these results with new experiments in
the next paper on kinetics in heterogeneous Fenton reaction.
where C0 is the initial concentration of AOII (mg · L-1), Ct is 3.2.2. TOC and COD Removal. Figure 6a shows the TOC
the concentration of AOII at different degradation times and COD conversion values versus reaction time obtained with
(mg · L-1), t is the degradation time (min), and kHFR is the several iron catalysts.
reaction rate constant (min-1). Comparing the behavior of nine iron containing catalysts, it
The reaction rate constants, which were obtained from the is important to evaluate the AOII elimination process, for
slopes of the straight lines, are displayed in Table 3. The example, if AOII removal occurs through adsorption, through
correlation coefficient R2 values were superior to 0.96 in all a chemical reaction or combination of both. For that reason,
cases, except to Fe-HT and Fe-CNF. The results revealed that several runs were then performed.
the rate constant for AOII were found to be in the order: Fe- In order to evaluate Fenton oxidation efficiency, the adsorp-
AC > Fe-CNF > Fe-CNT in carbon materials, Fe-S > Fe-SX > tion of AOII by supports materials has to be determined.
Fe-USY > Fe-MCM41 in siliceous materials, and Fe-SEP > Fe- Adsorption experiments were conducted under the same ex-
HT in clay materials. Generally, as it can be expected, the perimental conditions that those employed for catalytic runs with
adsorption capacity and active site number of catalyst increase heterogeneous Fenton catalysts. The final concentration of TOC
as catalyst dosage does. So, faster degradation of AOII could was measured after 120 min, as Figure 6b shows. This time is
be obtained as catalysts concentration is increased. considered enough to reach adsorption equilibrium. The ad-
502 Ind. Eng. Chem. Res., Vol. 49, No. 2, 2010

Figure 6. (a) Evolution of TOC and COD of AOII aqueous solution. (b) Removal of TOC (by adsorption and heterogeneous Fenton reaction) and COD of
AOII aqueous solution.

Figure 7. Toxicity removal and leaching of iron.

 Ind. Eng. Chem. Res., Vol. 49, No. 2, 2010 503

Figure 8. Comparison between pH 3 and 7 with Fe-SEP catalyst with several

parameters. Figure 10. Comparison of homogeneous and heterogeneous Fenton reaction
of AOII aqueous solutions with Fe-SEP.
Table 4. Iron Amount in Several Catalysts and Leaching after
Heterogeneous Fenton Reaction
In conclusion, the TOC and COD removal is by adsorption
catalyst Feinitial2+ (%) leaching (%) on the support mainly, whereas the catalytic oxidation is by
Fe-HT 4.7 25.6% siliceous and clays materials.
Fe-USY 4.8 21.0% 3.2.3. Toxicity. An early study of organic compounds from
Fe-AC 4.3 58.3% a dye manufacturing plant wastewater revealed the presence of
Fe-S 4.7 28.5%
several toxic chemicals.2 More recently, a textile azo dye
Fe-MCM 4.8 13.5%
Fe-X 4.8 18.3% processing plant effluent was identified as a major source of
Fe-CNT 4.3 29.3% mutagenic activity.19 These results underscore the need for
Fe-CNF 4.2 27.0% proper treatment of the dye wastewater prior to discharging it
Fe-SEP 4.9 14.7% into the environment. Pertinent to this issue is the question of
whether heterogeneous Fenton reaction is capable of mitigating
sorbed TOC was 68% for CNF, 62% for CNT, and 60% for the toxicity of the dye effluent.
active carbon. The adsorption of TOC by the zeolite USY, silica
xerogel, and sepiolite could be negligible in comparison with Toxicity data are often quantified in terms of the parameter
Fenton oxidation. To conclude, TOC removal by adsorption is EC50, which is the effective concentration of a toxin causing
more important in supports as HT, AC, CNT, and CNF than in 50% reduction in luminescent light emission in the assay (Figure
siliceous supports and clays minerals such as sepiolite. 7). Thus, the toxicity removal for AOII was found to be in the
The TOC and COD removal was conducted using nine order Fe-SEP > Fe-AC > Fe-HT > Fe-CNF > Fe-CNT > Fe-S
heterogeneous Fenton catalysts under the same experimental > Fe-SX > Fe-USY > Fe-MCM41 at an initial dye concentration
conditions, as explained before to assess the relative catalytic of 50 mg · L-1. Good detoxification (but not mineralization) was
activity of iron catalysts samples. The results are shown in obtained in these cases.
Figure 6b. As it can be clearly seen, hydrotalcite, active carbon, 3.2.4. Leaching. Leaching of the catalytic active species or
silica, and sepiolite were highly effective to treat the effluent poisoning of the active sites or fouling of the catalyst surface
after 120 min of reaction. Zeolite USY, MCM41, and silica by intermediate reaction products are important factors, which
xerogel gave a moderate TOC reduction of about 57-55% and determine the stability and durability of the catalyst.
COD reduction of about 45-64%. For the rest of the catalysts In order to evaluate the leaching of active species (iron) to
tested (CNT and CNF), degradation was comparable to that of the liquid phase that may become a second pollution source
the respective adsorption run, at about 65% and 75% for TOC and an important catalytic deactivation factor that has to be
and COD, respectively. After 120 min, the low value reached avoided, the iron metal was measured in terms of leaching for
by the COD/TOC ratio suggests the presence of low chain all experiments and the results are summarized in Table 4. The
organic acids. lower value of Fe content remaining in the solid phase after

Figure 9. (a) Comparison between fresh and used Fe-SEP catalyst. (b) Influence of the presence of carbonate ions on several parameters.
504 Ind. Eng. Chem. Res., Vol. 49, No. 2, 2010
Figure 11. Compounds detected in raw textile wastewater and removal of TOC, COD, and toxicity and color with Fe-SEP catalyst.
reaction (leaching) corresponds to activated carbon in compari-
son with CNT 29.3% and CNF 27.0%, in carbonaceous
materials.
The loss of active phase, leaching, decreases in the order AC
> CNT > S > CNF > HT > USY > SX > MCM41 ∼ SEP as
shown in Figure 7. Fe-SEP is the catalyst that shows the least
leaching, only 14.3%.
The actual heterogeneity of the catalysis over Fenton type
catalysts in the H2O2 solutions has often been a matter of
discussion. Tatiboüet et al.20 observed that both heterogeneous
(Fe-clays) and homogeneous (iron ions) Fenton catalysts show
similar behavior. However, heterogeneous catalysts are less
sensitive to the pH and more efficient in total organic carbon
(TOC) abatement. According to this study and others, the
heterogeneous Fenton process could proceed effectively with
Fe-SEP as the catalyst at pH 7 (Figure 8). The difference
between fresh and used Fe-SEP catalyst was only 6% in TOC
and toxicity removal (Figure 9a).
On the other hand, carbonates play an important role as
scavengers of OH radicals in natural systems. To verify the
presumption that the free radical reaction is dominant in the
heterogeneous Fenton decolorization reaction, a simple test was
conducted to identify whether the free radicals are involved
during the reaction. Carbonate is an effective radical scavenger.21
The presence of carbonates ions [10-3 M] with Fe-SEP catalyst
decreased the color and TOC removal efficiencies of AOII
(Figure 9b). This observation confirms the presumption that the
heterogeneous Fenton decolorization reaction of AOII is domi-
nated by free radical chain reaction.
In the presence of bicarbonate-carbonate ions, part of the
hydroxyl radicals reacts to form carbonate ion radicals, CO3-.
The kinetics and mechanisms of carbonate radicals with organic
compounds are poorly understood, and there are enough data
to suggest that these radicals may react with the organic
compounds. These reactions are, however, more selective than
those of the hydroxyl radical and the constants are lowershow
much lower depends on the nature of the organic compound.22
Thus, at pH 7, the rate constant of the reaction between the
carbonate radical and generally quite unreactive benzene is only
3 × 103 M-1 s-1, while that with phenol, which is known to be
more reactive than benzene, is 4.9 × 106 M-1 s-1.
3.3. Comparison of the Performances of Homogeneous
and Heterogeneous Catalyst. Heterogeneous catalysts show
higher TOC removal efficiency than homogeneous catalysts,
despite the fact that the later are faster in a shorter reaction
time. Figure 10 shows the conversion of AOII with homoge-
neous Fe2+ ions as compared with that obtained for heteroge-
neous Fe-SEP catalyst. A fast conversion of AOII is noted in
both samples. For a similar iron amount, homogeneous and
heterogeneous Fenton catalysts have similar catalytic perfor-
mance. However, it should be pointed out that the homogeneous
Fenton process has a significant disadvantage, the removal of
the sludge containing Fe ions at the end of the wastewater
treatment is expensive and needs a large amount of chemicals
and manpower.
3.4. Heterogeneous Fenton Reagent of Real Textile Waste-
water. Textile wastewater can be considered a very complex
matrix, composed by the effluents of washing, bleaching, and
dyeing processes. Release of dye and pigment compounds from
textile manufacturing processes may cause environmental pol-
lution. High contents of inorganic salts are found in textile
wastewater, and many of them, such as chlorides, sulphates,
carbonates, and phosphates, decrease the efficiency of the Fenton
processes. These species lower the speed of the reactions
mediated by hydroxyl radical and can also compete for active
sites. In this sense, Figure 11 shows the main intermediates
detected in real wastewater by GC-MS. HFP with Fe/sepiolite
of real wastewater shows decolorization, TOC, COD, and
toxicity removal efficiency that are very close to 25, 36 and
24% in 120 min, respectively, which shows that the Fe-SEP
catalyst exhibits a moderate catalytic activity when a complex
matrix is present.
The COD/TOC ratio initially has a value of 3.03 and
decreases to reach a value of 1.44 after 2 h of reaction (Fe-
SEP). This is consistent with the expected evolution of the
organic matter remaining in the textile wastewater toward
increasingly oxidized species. The low value reached by the
COD/TOC ratio suggests an important relative presence of low
chain organic acids, including carboxylic acids.3 HFP can be
considered as a promising option for a pretreatment step in the
treatment of these industrial effluents.
4. Conclusions
Nine heterogeneous Fenton type catalysts based on different
supports and iron were prepared and tested with a model
compound, AOII, and a real textile wastewater. Hydrotalcite
and activated carbon showed the highest activity in color, TOC,
COD, and toxicity reduction of AOII solutions, mainly by
adsorption. The Fe catalyst supported on sepiolite showed to
be a viable alternative as heterogeneous catalyst in the total
abatement of toxic organic load due to AOII, a dye present in
significant amounts in textile wastewaters. Leaching of iron was
observed, mainly in carbon materials.

Acknowledgment
The authors gratefully acknowledge the financial support from
Ministerio de Educación y Ciencia by the CONSOLIDER
Program through TRAGUA Network CSD2006-44, CTQ2008-
02728, by Comunidad de Madrid through REMTAVARES
Network S-505/AMB/0395, and by Complutense/Santander
project PR34/07-15913. We also thank R. López for your
assistance in experiment preparation.
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ReceiVed for reView July 31, 2009
ReVised manuscript receiVed October 9, 2009
Accepted October 18, 2009
IE901212M