Technical Note

Oxidation of Orange G by persulfate activated by Fe(II), Fe(III) and zero

valent iron (ZVI)
S. Rodriguez

, L. Vasquez, D. Costa, A. Romero, A. Santos

Dpt. Ingenieria Qumica, Facultad Qumicas, Universidad Complutense, 28040 Madrid, Spain
h i g h l i g h t s
Oxidation of Orange G (azo dye) with iron activated persulfate was studied.
An oxidation pathway was proposed for OG oxidation by activated persulfate.
The inuence of iron valence (0, II and III) on the activity was studied.
Product distribution, mineralization and detoxication were also studied.
a r t i c l e i n f o
Article history:
Received 30 July 2013
Received in revised form 11 December 2013
Accepted 12 December 2013
Available online 16 January 2014
Keywords:
Dye
Orange G
Persulfate
Oxidation pathway
Iron valence
Ecotoxicity
a b s t r a c t
Persulfate (PS) was employed in the oxidation of Orange G (OG), an azo dye commonly found in textile
wastewaters. Activation of PS was conducted with iron to generate sulfate free radicals (SO

4
) with high
redox potential capable to oxidize most of the organics in water. Identication of oxidation intermediates
was carried out by analyzing at different times organic by-products generated from treatment of a con-
centrate dye solution (11.6 mM) with 153 mM of PS and 20 mM of Fe(II) at 20 C. Intermediate reaction
products (mainly phenol (PH) and benzoquinone (BQ), and in less extent aniline, phenolic compounds
and naphthalene type compounds with quinone groups) were identied by GC/MS and HPLC, and an oxi-
dation pathway was proposed for the oxidation of OG with iron activated PS. The effect of iron valence (0,
II and III) in the oxidation of an aqueous solution of OG (containing 0.1 mM) was studied in a 0.5 L batch
reactor at 20 C. Initial activator and PS concentrations employed were both 1 mM. Complete pollutant
removal was achieved within the rst 30 min when iron II or III were employed as activators. Quinone
intermediates generated during pollutant oxidation may act as electron shuttles, allowing the reduction
of Fe(III) into Fe(II) in the redox cycling of iron. Therefore, activation of PS by Fe(III) allowed complete OG
removal. When zero valent iron (ZVI) was employed (particle diameter size 0.74 mm) the limiting step in
SO

4
generation was the surface reaction between ZVI and the oxidant yielding a lower oxidation rate of
the dye. An increase in the oxidant dosage (0.2 mM OG, 2 mM Fe(III) and 6 mM PS) allowed complete
pollutant and ecotoxicity removal, as well as mineralization close to 75%.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Textile industries generate considerable amounts of wastewa-
ters polluted with dyes (over 1 Mt of different dyes produced
annually in the world (Peng et al., 2008). Among them, azo dyes
(with a chromophore group AN@NA) can be considered one of
the most important commercial dyes as they represent around
60% of the world market for dyes used by the textile industries
(Kunz et al., 2002; Azam and Hamid, 2006). However, their poten-
tial disadvantages from an environmental point of view such as
toxicity, non-biodegradation and carcinogenic potential must be
taken into account (Chen et al., 2003; Peng et al., 2008). Therefore,
the removal of these kinds of pollutants is of great interest, since
conventional biological treatment technologies are not able to do
it efciently.
Several advanced oxidation processes, employing Fenton s
Reagent (Fernandez et al., 1999; Xu et al., 2004; Hsueh et al.,
2005), TiO

2
mediated photocatalysis (Vinodgopal et al., 1996; Xie
and Li, 2006; Yu et al., 2008), potassium permanganate (Xu et al.,
2005; Aleboyeh et al., 2009) and oxone/Co
2+
reagent (Fernandez
et al., 2004), have been examined for the degradation of dyes. Re-
cently, PS (S
2
O
2
8
), a strong two-electron oxidizing agent with a re-
dox potential of 2.01 V, has proved to be efcient in textile dyes
removal (Kusic et al., 2011). Moreover, PS is typically activated to
generate reactive SO

4
(Liang et al., 2004a; Rodriguez et al., 2012)
with oxidationreduction potential of 2.6 V (Berlin, 1986), which
can oxidize most of the organics in water. Besides of the high redox
0045-6535/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2013.12.037

Corresponding author. Tel.: +34 913944173.

E-mail address: srvega@quim.ucm.es (S. Rodriguez).
Chemosphere 101 (2014) 8692
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potential of SO

4
, PS can be attractive for application in chemical
oxidation due to its high solubility in water (2.5 M at 20 C), high
stability and relative low cost. PS can be thermally or chemically
activated, either by pH adjustment, or employing transition metals
(Huang et al., 2002; Liang et al., 2003, 2004a, 2004b). Metal activa-
tion takes place using a divalent metal, usually iron, as shown in
Eq. (1).
S
2
O
2
8
Me
n
!SO

4
Me
n1

SO
2
4
1
If Fe(II) is employed as activator, the overall reaction between
iron and PS would be described by Eq. (2) while undesired unpro-
ductive radical consumption occurs through Eq. (3).
S
2
O
2
8
Fe
2
!Fe
3
SO
2
4
SO

4
2
SO

4
Fe
2
!Fe
3
SO
2
4
3
Therefore, PS activation by Fe(II) may be limited by the SO

4
scavenging due to excessive iron according to this reaction (Liang
et al., 2004a; Liang et al., 2007; Vicente et al., 2011). Liang and
Guo (2010) reported that the zero-valent iron (ZVI) could be used
as a releasing source of ferrous iron through the corrosion by PS
(Eq. (4)).
Fe
0
S
2
O
2
8
!Fe
2
2SO
2
4
4
In addition to this oxidation reaction, two other oxidation path-
ways may take place. One, depending on the oxidation of ZVI by
ferric ion; and another mediated by the H
+
corrosion of ZVI (Eqs.
(5) and (6))
2Fe
3
Fe
0
!3Fe
2
5
Fe
0
2H

!Fe
2
H
2
6
The pH increase promotes the formation of precipitated iron
hydroxide on ZVI, which may eventually form a layer on the sur-
face metal and inhibit its reactivity (Chen et al., 2001). In this work,
oxidation by Iron Activated PS of OG, a typical azo dye in textile
wastewaters has been studied in order to analyze the oxidation
route and the inuence of iron valence on the activity and product
distribution. Besides, mineralization and detoxication (by using
Microtox bioassay) with the reaction progress were studied.
2. Experimental
2.1. Materials
Analytical reagent grade or better chemicals as well as Milli-Q
water were used in the experiments. OG, whose chemical structure
can be seen in Fig. SM-1 of Supplemental Material (SM), was pur-
chasedfromAcros andsodiumPS was obtainedfromSigmaAldrich.
Ferrous and ferric sulfate obtained fromFluka, as well as ZVI (parti-
cle diameter 0.74 mm) from Aldrich were used as the activator iron
species. Acetonitrile from Riedel de Han was employed in mobile
phase in HPLC determinations. Finally, the microorganisms em-
ployed for ecotoxicity measurements (Photobacterium Phosphore-
um) were Microtox Acute Reagent supplied by I.O. Analytical.
2.2. Oxidation runs
Reactions were carried out in a 0.5 L batch reactor at 20 C.
Experimental runs carried out are summarized in Table 1. OG solu-
tions were adjusted to acid pH (3.5) with H
2
SO
4
. Following PS and
iron were added.
Run 1 was carried out using a solution of 11.6 mM of OG with
addition of 20 mM of Fe(II) and 153 mM of PS. This high amount
of dye was convenient for better identication of the oxidation
products in OG oxidation with PS activated by Fe(II). This reaction
was triplicated to analyze the reaction media at three reaction
times. A 250 mL dye solution after partial oxidation in Run 1 was
extracted with a total volume of 100 mL of dichloromethane for
3 times. Then the extracts were concentrated to about 5 mL by
rotary evaporator at 40 C before being used for GCMS analysis.
Runs 24 were carried out to study the effect of iron valence (II,
III and 0) on the oxidation of an aqueous solution 0.1 mM in OG, by
using 1 mM of PS and 1 mM of activator. A blank experiment (Run
5) was also conducted in absence of iron at the same PS concentra-
tion (1 mM) to analyze if PS can degrade the dye without activa-
tion. Run 6 was conducted to study the oxidation of an identied
product, BQ. In this run a solution 0.05 mM BQ was treated with
3 mM PS activated by 3 mM Fe(III)

Finally, in order to analyze

the inuence of both oxidant and activator concentration in the
mineralization achieved and the evolution of intermediates gener-
ated during the OG oxidation, Run 7 was carried out. A higher rela-
tion of oxidant/dye (6:0.2 mM) than used in Runs 24 was
employed. Besides, activator used (Fe(III)) was also added in Run
7 at a double concentration than used in Run 4.
2.3. Analytical
Liquid samples were withdrawn periodically and analyzed. For
the determination of the concentration of OG in aqueous phase, a
UVVis, BOECO brand, model S20 spectrophotometer was em-
ployed. The characteristic wavelength for this compound is
478 nm. Intermediate reaction products from Run 1 were identi-
ed by GC/MS (HP 6890N MSD 5975B). A HP-5 column
(30 m 0.32 mm internal diameter 0.25 lm) was used for the
analysis. Analysis was performed in a temperature programmed
mode with an initial temperature of 40 C held for 10 min, temper-
ature increase ramp up to 100 C with a 12 C min
1
rate, then to
200 C with 5 C min
1
, and nally ramp to 270 C with a
20 C min
1
rate followed by an isothermal time of 5 min (Zhong
et al., 2011).
Oxidation intermediates identied by GC/MS were also quanti-
ed by HPLC (HewlettPackard, mod. 1100) using a Diode Array
detector (HP G1315A) with a Chromolith Performance column
(monolithic silica in rod form, RP-18e 1004.6 mm) as the station-
ary phase and a 90/10 (v/v) mixture of H
2
SO
4
1 mM and acetoni-
trile as the mobile phase. The ow rate of the mobile phase was
1 mL min
1
. The concentration of PS in solution was determined
by titration using a solution of KMnO
4
, of known concentration,
in sulfuric acid using a titrimetric volumetric analyzer supplied
by Metrohm. Dissolved iron concentration was measured by a
Microwave Plasma Atomic Emission Spectrometer (Agilent 4100
MP-AES). The remaining organic content (TOC) was measured
using a Shimadzu TOC-V CSH analyzer by oxidative combustion.
The sample was introduced into the combustion furnace operated
at 680 C in the presence of a Pt/Al
2
O
3
catalyst, that allowed com-
plete sample combustion generating CO
2
. After dehumidication
Table 1
Experimental runs carried out in OG oxidation by PS.
Run [OG] mM [PS] mM [Fe] mM Fe valence [BQ] mM
1 11.6 153 20 2
2 0.1 1 1 2
3 0.1 1 1 3
4 0.1 1 1 0
*

5 0.1 1
6 3 2 3 0.05
7 0.2 6 2 3
*
Particle diameter used for ZVI (Run 4) was 0.74 mm.
S. Rodriguez et al. / Chemosphere 101 (2014) 8692 87
and halogen removal in a scrubber, non-dispersive infrared spec-
troscopy was employed for quantication. Total nitrogen amount
was measured by oxidatively combustionchemiluminescence
method. The associated TNM-1 module coupled to the total organic
carbon analyzer TOC-V was employed. The nitrogen content of the
sample was completely oxidized to NO and taken to the chemilu-
minescence detector TNM-1 for quantication. An enzymatic kit
(Enzytec Oxalic Acid) was employed for oxalic acid determinations
by oxidation of this compound by oxalate oxidase forming a blue
quinone compound. The intensity of color was measured at
590 nm.
The ecotoxicity of liquid samples was determined by means of a
bioassay following the standard Microtox test procedure (ISO
11348-3, 1998) using a Microtox M500 Analyzer (Azur Environ-
mental) based on the decrease of light emission by P. Phosphoreum
upon exposure to a toxic media. Inhibition of the light emitted by
the bacteria was measured after 15 min contact time. Before mea-
suring the ecotoxicity, the pH values of all samples were re-ad-
justed to between 6 and 7 in order to prevent a pH effect.
Unreacted PS has to be neutralized, since the EC
50
value for this
oxidant is 106 mg L
1
(Rodriguez et al., 2011). For this, a stoichi-
ometric amount of sodium bisulte of the remaining PS was added.
A more detailed description of the ecotoxicity measurements can
be found elsewhere (Santos et al., 2006).
3. Results and discussion
Reaction intermediates generated in OG oxidation with PS acti-
vated by Fe(II) (Run 1) were identied by GC/MS. Phenolic com-
pounds were mostly obtained, while aniline and naphthalene
type compounds with quinone groups were also detected in less
extent. Identied intermediates were subsequently quantied by
HPLC. The main intermediates quantied were PH and BQ and, in
less amount, ftalic acid, catechol, hydroquinone (HQ), naphthoqui-
none and organic acids (oxalic, fumaric and maleic acid). A GC/MS
chromatogram of OG oxidation products obtained in Run 1 can be
seen in Fig. SM-2 of SM. Based on the main intermediates identi-
ed, and according to the results previously described (Zhong
et al., 2011), a possible degradation pathway of OG by PS activated
by Fe(II) is proposed and shown in Fig. 1, and the corresponding
chemical names of the intermediates are shown in Table 2.
The rst step of OG degradation is the breakage of the N@N
bound, resulting in the production of 1,3-Naphtalenedisulfonic-
acid,8-amino-7-hydroxy, and aniline. Aniline can then be degraded
into PH which is further oxidized into BQ. On the other hand, 1,3-
Naphtalenedisulfonicacid,8-amino-7-hydroxy can split into naph-
thalene derivatives as reported by other authors (Zhong et al.,
2011). A subsequent degradation into phthalic acid derivatives
and other benzene-type intermediates may occur. As nal degra-
dation intermediates short chain acids (as oxalic, fumaric or maleic
acid) were detected. By analysis of total nitrogen, it was found that
only 15% of nitrogen in the initial OG was oxidized to N
2
.
Intermediates detected, oxidant and pollutant conversion were
also quantied with time using several iron sources as activator:
Fe(II), Fe(III) and Fe(0) (Runs 24 in Table 1). As an example, HPLC
chromatograms of OG oxidation obtained in Run 2 can be seen in
Fig. SM-3 of SM. Results obtained in the oxidation of OG by acti-
vated PS in Runs 2, 3 and 4 are shown in Fig. 2, where both OG
and PS conversions are plotted (2a and 2b respectively), as well
as dissolved iron (Fig. 2c) when ZVI was employed. Complete pol-
lutant removal was achieved within the rst minutes when both
Fe(II) and Fe(III) were employed as activator. When Fe(II) was used
(Run 2) SO

4
, capable of pollutant oxidation, are quickly generated
through Eq. (2), with a quick rise in PS conversions corresponding
to reaction (2). When Fe(III) was employed as PS activator, OG was
also removed from the media, even though SO

4
can only be gener-
ated when Fe(II) is employed as activator (Eq. (2)). An explanation
to this phenomenon can be found in the oxidation pathway pro-
posed for OG oxidation by activated PS (Fig. 1), were both BQ
and HQ are generated as oxidation intermediates.
In some studies employing Fenton s reagent it has been reported
the inuence of certain organic compounds and/or their degrada-
tion products on the reactivity of iron (Chen and Pignatello,
1997; Duesterberg et al., 2005). Some organic compounds act as
electron transfer agents toward iron being able to reduce Fe(III)
into Fe(II) (Duesterberg et al., 2005). Quinone compounds as HQ
and BQ can reduce Fe(III) into Fe(II) at low pHs by this quinone cy-
cle, as described in Eqs. (7)-(9) (Chen and Pignatello, 1997). Thus,
this reagenerated Fe(II) can react with PS to generate SO

4
.
Therefore, activation of PS by Fe(III) allowed complete OG re-
moval while Fe(II) is continuously produced from Fe(III) recycled
by the quinone-HQ intermediates produced. Following, reaction
(2) takes place and supplies the strong oxidant sulfate radicals. Be-
sides, oxidation of OG directly with Fe(III) without PS was not ob-
served. While the initial SO

4
production using Fe(III) is lower than
that found using Fe(II) a slow increase in PS conversion is noticed
in Run 3 in relation to that observed in Run 2. Activation by Fe(III)
was not observed when, as an example, diuron was employed as
target pollutant (Vicente et al., 2011), since in this last case, elec-
tron shuttle intermediates were not generated and therefore Fe(II)
could not be regenerated. When using ZVI about 3 h were required
for complete OG removal. As can be seen in Fig. 2c, at this reaction
time the dissolved iron was only 0.2 mM (20% of the total ZVI
added) and PS conversion was about 40%. Therefore, the limiting
step using ZVI as activator was the surface reaction between ZVI
and the oxidant, described through Eqs. (4)(6) (Liang and Guo,
2010).
Fig. 3 represents the ratio of the carbon concentration of the
intermediate compounds quantied in Runs 24 (C
i
, mM) and
the initial carbon concentration of OG (C
OG0
, mM). As can be seen,
PH and BQ were the main intermediates obtained. Low amounts of
aniline were detected as it was quickly oxidized to PH, proles
88 S. Rodriguez et al. / Chemosphere 101 (2014) 8692
obtained corresponded to a serial step intermediate. Traces of HQ,
catechol, naftoquinone, ftalic acid, and organic acids were also de-
tected. When Fe(II) was employed as activator (Run 2), a quick ini-
tial oxidation takes place, and therefore rst intermediates, as PH,
are quickly generated and PS is rapidly consumed at initial stages
and unproductive consumption of the SO

4
initially formed (reac-
tion (3)) is also favored by using Fe(II). Therefore, the oxidation
reactions are ended achieving a plateau in PH and BQ at short
times.
On the contrary, in Runs 3 and 4 it is noticed that PH increases
at short times, achieves a maximum and decreases remarkably at
longer times, with a corresponding increase in BQ concentration
as PH diminishes, as expected for the serial reaction in Fig. 1. PH
prole in Runs 3 and 4 (shown in Fig. 3b and c, respectively) can
be explained by the lower initial release of SO

4
and consequently,
lower PS conversion with time than found in Run 2. The maximum
obtained in PH prole with time is then obtained at longer reaction
times in Runs 3 and 4. This fact is especially perceptible when ZVI
is employed, since oxidation with this activator is remarkably
slower.
BQ proles with Fe(III) also achieved a plateau at 120 min., as
can be seen in Fig. 3b, while this compound continuously increased
with ZVI (Fig. 3c). This could be explained considering the highest
conversion of oxidant achieved with Fe(III) in relation to that found
with ZVI at the time interval studied. Short chain acids proles
with time slightly increased at high reaction times, as corresponds
to end intermediates. These intermediate proles are in agreement
with proposed oxidation pathway for OG oxidation with activated
NH
2
OH
N
N
OH
SO
3
Na
SO
3
Na
NH
NH
OH
SO
3
Na
SO
3
Na
NH
2
OH
SO
3
Na
SO
3
Na
OH
OH
OH
O
O
O
O
O
O
O
O
O
O
O
O OH
O H
+
(1)
(2)
(3) (4)
(5)
(6) ) 9 ( ) 7 (
(10)
O
O
(12)
OH
OH
OH
OH
(8)
COOH
COOH
(13) (11)
H
H O
O H
O
OH
(15) (14)
O
OH O
O H
(16)
Fig. 1. Oxidation pathway of the oxidation of OG with iron activated PS.
S. Rodriguez et al. / Chemosphere 101 (2014) 8692 89
PS (Fig. 1). TOC removal in Runs 24 was below 10%, and therefore
high amounts of non-identied compounds remained in the media.
A non-identied compound with absorption spectra maximum at
210 and 258 nm was identied by HPLC, corresponding probably
to quinone type condensation intermediates. Ecotoxicity measured
after 4 h of reaction in Runs 24 (with TUs of 18, 26 and 20 equitox
m
3
respectively) was slightly higher than that corresponding to
identied toxic compounds remaining in the media, mostly BQ,
with an EC
50
value of 0.1 mg L
1
(calculated TU values of 17, 18
and 17, respectively corresponding to the sum of each intermedi-
ate concentration divided by its EC
50
value). Therefore, it can be
concluded that nonidentied intermediates are non-toxic, at least
for this bioassay.
To elucidate if BQ is a refractory compound to PS oxidation or if
it could be removed from the media with higher amounts of oxi-
dant a further experiment (Run 8 in Table 1) was conducted to
study the oxidation of BQ with PS activated by Fe(III). Results ob-
tained are shown in Fig. 4. As can be seen, a continuous slow BQ
removal was observed. HPLC analysis over different reaction times
showed no aromatic intermediates in BQ oxidation. After 24 h
reaction, complete BQ removal was achieved. Microtox assay
conrmed complete detoxication after 24 h of reaction, and
Table 2
Reaction intermediates in Fig. 1.
Number Chemical name Molecular
formula
1 1,3-Naphtalenedisulfonicacid,8-amino-7-
hydroxy, sodiumsalt
C
10
H
7
Na
2
NO
7
S
2
2 Aniline C
6
H
5
NH
2
3 2-Naphthalenol C
10
H
8
O
4 1,2-Naphthalenediol C
10
H
8
O
5 Phenol C
6
H
6
O
6 1,2-Naftoquinone C
10
H
6
O
2
7 2H-1-Benzopyran C
9
H
5
O
2
8 Catechol C
6
H
6
O
2
9 Hidroquinone C
6
H
6
O
2
10 Phtalic anhydride C
8
H
4
O
3
11 Indan-1,2,3-trione C
9
H
4
O
3
12 Benzoquinone C
6
H
4
O
2
13 Maleic acid C
4
H
4
O
4
14 Phthalic acid C
8
H
6
O
4
15 Fumaric acid C
4
H
4
O
4
16 Oxalic acid C
2
H
2
O
4
0.0
0.2
0.4
0.6
0.8
1.0
Run OG (mM) PS (mM) Fe (mM) Val
2 0.1 1 1 2
3 0.1 1 1 3
4 0.1 1 1 0
X
O
G
0.0
0.2
0.4
0.6
0.8
1.0
X
P
S
0 50 100 150 200 250
0.0
0.2
0.4
0.6
0.8
1.0
C
F
e

(
m
M
)
t (min)
(a)
(b)
(c)
Fig. 2. Inuence of the valence of iron added at zero time on (a) pollutant
conversion (b) remaining persulfate and (c) dissolved iron concentration.
[OG]
0
= 0.1 mM, [PS]
0
= 1 mM, [Fe]
0
= 1 mM. T = 20 C.
0.00
0.02
0.04
0.06
0.08
0.10
C
I
n
t
e
r
m
e
d
i
a
t
e
/
C
O
G
0
0.00
0.02
0.04
0.06
0.08
0.10
C
I
n
t
e
r
m
e
d
i
a
t
e
/
C
O
G
0
0 50 100 150 200 250
0.00
0.02
0.04
0.06
0.08
0.10 Key Intermediate
Phenol
Benzoquinone
Maleic A.
Fumaric A.
Naftoquinone
Ftalic A.
Catechol
Hidroquinone
t (min)
C
I
n
t
e
r
m
e
d
i
a
t
e
/
C
O
G
0
(a)
(b)
(c)
Fig. 3. Inuence of the valence of iron added at zero time on intermediate
compounds obtained employing (a) Fe
2+
(b) Fe
3+
and (c) ZVI. [OG]
0
= 0.1 mM,
[PS]
0
= 1 mM, [Fe]
0
= 1 mM. T = 20 C.
90 S. Rodriguez et al. / Chemosphere 101 (2014) 8692
therefore, no toxic intermediates were present in the media. There-
fore, oxidation of BQ does not produce toxic compounds.
In order to clarify if TOC conversion from non-identied com-
pounds in Runs 24 can be improved, Run 9 was accomplished,
employing 0.2 mM OG, 2 mM Fe(III) and 6 mM PS, thus using high-
er ratios oxidant/pollutant and activator concentration than used
in Run 3. Results obtained are shown in Fig. 5. As can be seen,
about 35% of TOC removal was achieved in the rst 24 h, while al-
most 75% was obtained after 7 d. Moreover, toxicity obtained after
48 h reaction, when BQ was completely removed from the reaction
media, was negligible (TU < 1). Therefore, employing enough
amount of PS during a proper reaction time allows complete pollu-
tant and toxicity removal, as well as mineralization close to 75%.
4. Conclusions
Oxidation of OG, an azo dye commonly found in textile waste-
waters, was accomplished by PS activated with iron. Oxidation
pathway was proposed for the oxidation of OG with iron activated
PS based on the intermediates detected (mainly PH and BQ, and in
less extent aniline, phenolic compounds and naphthalene type
compounds with quinone groups). According to this pathway, oxi-
dation of OG occurs through two ways after a rst breakage into
aniline and 1,3-Naphtalenedisulfonicacid,8-amino-7-hydroxy. Ani-
line is quickly oxidized into PH which is further oxidized into BQ
while 1,3-Naphtalenedisulfonicacid,8-amino-7-hydroxy can gen-
erate naphthalene derivatives, phtalic acid derivatives and other
benzene-type intermediates. Short chain acids can be obtained as
nal degradation intermediates.
The effect of iron valence (II, III and 0) in the oxidation of OG
was also studied. Complete pollutant removal was achieved within
the rst 30 min when Fe(II) was employed as activator. Same re-
sults were obtained when PS was activated by Fe(III). Quinone
intermediates generated during pollutant oxidation may act as
electron shuttles, allowing the reduction of Fe(III) into Fe(II) in
the redox cycling of iron. Therefore, activation of PS by Fe(III) al-
lowed complete OG removal. The longer reaction time required
when ZVI was employed (at the iron particle diameter selected),
can be explained by the slow release of iron cation to the media
being the limiting step the surface reaction between ZVI and the
oxidant.
Almost negligible TOC removal was observed at the lowest oxi-
dant and activator dosages used. Remaining ecotoxicity was in
agreement with that expected from the BQ in the media. Increasing
the oxidant and activator concentrations, BQ and TOC remarkably
decreases being negligible the toxicity measured by the Microtox
bioassay. In any case, from the oxidation route found it is obvious
that the elimination of the dye is not enough but the abatement of
the toxic compounds appearing in the media must also be
achieved.
Acknowledgements
The authors acknowledge nancial support from Comunidad
Autonoma of Madrid (Project CARESOIL S2009AMB-1648) and
from Spanish Ministry of Economy and Competitiveness, Project
CTM2010-16693.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemosphere.
2013.12.037.
References
Aleboyeh, A., Olya, M., Aleboyeh, H., 2009. Oxidative treatment of azo dyes in
aqueous solution by potassium permanganate. J. Hazard. Mater. 162, 1530
1535.
Azam, A., Hamid, A., 2006. Effects of gap size and UV dosage on decolorization of C.I.
Acid Orange 7 by UV/H
2
O
2
process. J. Hazard. Mater. 133, 167171.
Berlin, A., 1986. Kinetics of radical-chain decomposition of persulfate in aqueous
solutions of organic compounds. Kinet. Catal. 27, 3439.
Chen, R., Pignatello, J., 1997. Role of quinone intermediates as electron shuttles in
fenton and photoassisted fenton oxidations of aromatic compounds. Environ.
Sci. Technol. 31, 23992406.
Chen, J., Al-Abed, S., Ryan, J., Li, Z., 2001. Effects of pH on dechlorination of
trichloroethylene by zero-valent iron. J. Hazard. Mater. 83, 243254.
Chen, K., Wu, J., Huang, C., Liang, Y., Hwang, S.H., 2003. Decolorization of azo dye
using PVA-immobilized microorganisms. J. Biotechnol. 101, 241252.
Duesterberg, C., Cooper, W., Waite, T., 2005. Fenton-mediated oxidation in the
presence and absence of oxygen. Environ. Sci. Technol. 39, 50525058.
Fernandez, J., Bandara, J., Lopez, A., Buffat, P., Kiwi, J., 1999. Photoassisted Fenton
degradation of nonbiodegradable azo dye in Fe-free solutions mediated by
cation transfer membranes. Langmuir 15, 185192.
Fernandez, J., Maruthamuthu, P., Renken, A., Kiwi, J., 2004. Bleaching and
photobleaching of Orange II within seconds by the oxone/Co
2+
reagent in
Fenton-like process. Appl. Catal. B Environ. 49, 207215.
Hsueh, C., Huang, Y., Wang, C., Chen, C., 2005. Degradation of azo dyes using low
iron concentration of Fenton and Fenton-like system. Chemosphere 58, 1409
1414.
Huang, K., Couttenye, R., Hoag, G., 2002. Kinetics of heat-assisted persulphate
oxidation of methyl tert-butyl ether (MTBE). Chemosphere 49, 413420.
Kunz, A., Peralta-Zamora, P., Moraes, S., Duran, N., 2002. Novas Tendncias no
tratamento de euentes txteis. Quim. Nova 25, 2578.
0 100 200 300 1500 2000 2500 3000
0.0
1.0
2.0
3.0
4.0
5.0
C
B
Q

(
m
g

L
-
1
)
Time (min)
Fig. 4. BQ oxidation with PS activated by Fe
3+
(Run 6) [BQ] = 0.05 mM, [Fe
3+
] =
2 mM, [PS] = 3 mM, T = 20 C.
0 1 2 3 4 5 6 7 8
15
20
25
30
35
40
C
T
O
C

(
m
g

L
-
1
)
Time (d)
Fig. 5. TOC prole versus time in OG oxidation by activated PS (Run 7).
[OG] = 0.2 mM, [Fe
3+
] = 2 mM, [PS] = 6 mM, T = 20 C.
S. Rodriguez et al. / Chemosphere 101 (2014) 8692 91
Kusic, H., Peternel, I., Ukic, S., Koprivanac, N., Bolanca, T., Papic, S., Loncaric Bozic, A.,
2011. Modeling of iron activated persulfate oxidation treating reactive azo dye
in water matrix. Chem. Eng. J. 172, 109121.
Liang, C., Guo, Y., 2010. Mass transfer and chemical oxidation of naphthalene
particles with zerovalent iron activated persulfate. Environ. Sci. Technol. 44,
82038208.
Liang, C., Bruell, C., Marley, M., Sperry, K., 2003. Thermally activated persulphate
oxidation of trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) in aqueous
systems and soil slurries. Soil Sediment Contam. 12, 207228.
Liang, C., Bruell, C., Marley, M., Sperry, K., 2004a. Persulfate oxidation for in situ
remediation of TCE. I. Activated by ferrous ion with and without a persulfate-
thiosulfate redox couple. Chemosphere 55, 12131223.
Liang, C., Bruell, C., Marley, M., Sperry, K., 2004b. Persulphate oxidation for in situ
remediation of TCE II. Activated by chelated ferrous ion. Chemosphere 55,
12251233.
Liang, C., Huang, C.F., Mohanty, N., Lu, C., Kurakalva, R., 2007. Hydroxypropyl-beta-
cyclodextrin-mediated iron-activated persulfate oxidation of trichloroethylene
and tetrachloroethylene. Ind. Eng. Chem. Res. 66, 64666479.
Peng, Y., Fu, D., Liu, R., Zhang, F., Liang, X., 2008. NaNO
2
/FeCl
3
catalyzed wet
oxidation of the azo dye Acid Orange 7. Chemosphere 71, 990997.
Rodriguez, S., Santos, A., Romero, A., Vicente, F., 2012. Kinetic of oxidation and
mineralization of priority and emerging pollutants by activated persulfate.
Chem. Eng. J. 213, 225234.
Santos, A., Yustos, P., Rodriguez, S., Garcia-Ocho, F., 2006. Wet oxidation of phenol,
cresols and nitrophenols catalyzed by activated carbon in acid and basic media.
Appl. Catal. B Environ. 65, 269281.
Vicente, F., Santos, A., Romero, A., Rodriguez, S., 2011. Kinetic study of diuron
oxidation and mineralization by persulphate: effects of temperature, oxidant
concentration and iron dosage method. Chem. Eng. J. 170, 127135.
Vinodgopal, K., Wynkoop, D., Kamat, P., 1996. Environmental photochemistry on
semiconductor surfaces: photosensitized degradation of a textile azo dye, Acid
Orange 7, on TiO
2
particles using visible light. Environ. Sci. Technol. 30, 1660
1666.
Xie, Y., Li, X., 2006. Interactive oxidation of photoelectrocatalysis and electro-Fenton
for azo dye degradation using TiO
2
Ti mesh and reticulated vitreous carbon
electrodes. Mater. Chem. Phys. 95, 3950.
Xu, X., Li, H., Wang, W., Gu, J., 2004. Degradation of dyes in aqueous solutions by the
Fenton process. Chemosphere 57, 595600.
Xu, X., Li, H., Wang, W., Gu, J., 2005. Decolorization of dyes and textile wastewater
by potassium permanganate. Chemosphere 59, 893898.
Yu, Z., Keppner, H., Laub, D., Mielczarski, E., Kiwi-Minsker, L., Renken, A., Kiwi, J.,
2008. Photocatalytic discoloration of Methyl Orange on innovative parylene-
TiO
2
exible thin lms under simulated sunlight. Appl. Catal. B Environ. 79,
6371.
Zhong, X., Royer, S., Zhang, H., 2011. Mesoporous silica iron-doped as stable and
efcient heterogeneous catalyst for the degradation of C.I. Acid Orange 7 using
sonophoto-Fenton process. Sep. Purif. Technol. 80, 163171.
92 S. Rodriguez et al. / Chemosphere 101 (2014) 8692