Res. Chem. Intermed., Vol. 29, No. 3, pp.

307 316 (2003)

VSP 2003.
Also available online - www.vsppub.com

Hydroxyl radical-mediated advanced oxidation processes

for textile dyes: a comparison of the radiolytic and
sonolytic degradation of the monoazo dye Acid Orange 7
K. VINODGOPAL and JULIE PELLER
Department of Chemistry, Indiana University Northwest, Gary, IN 46408, USA
Received 18 January 2003; accepted 22 January 2003
AbstractAcid Orange 7, a textile azo dye, has been partially mineralized and degraded using
-radiolysis and sonolysis. These two different advanced oxidation processes (AOP) are effective in
producing . OH radicals and cause complete destruction of the chromophore. The reaction mechanism
of dye degradation has been probed by analyzing the reaction products with HPLC. In both cases,
the nal end products of degradation are oxalate and formate ions. The intermediates observed are
all similar. While hydroxybenzenesulfonic acid is the major observed reaction intermediate in the
oxidation processes, the pulse radiolysis studies indicate that the OH radical initiated pathway for
attack occurs via the initial formation of 1,2-naphthaquinone and subsequent breakdown into oxalic
acid.
Keywords: Sonolysis; radiolysis; azo dyes; hydroxyl radical; advanced oxidation.

INTRODUCTION

Advanced oxidation processes (AOPs) using hydroxide radicals as the primary

oxidant have emerged as a promising new technology for the degradation of organic
pollutants. These AOPs include semiconductor-based photocatalysis, sonolysis and
-radiolysis, and in recent years serious consideration has been given to these
methods for treating textile dye wastes. Azo dyes are by far the single largest
group of dyes produced worldwide. They are ubiquitous commercial chemicals
that present unique environmental problems arising from their ability to resist
degradation under most conditions [1 3]. The largest discharge of these colorants
into the environment occurs via the dye ef uents from textile mills and other
industries that use them. It is quite likely that signi cant restrictions on the discharge
of such colorant material into municipal wastewater streams will be passed in the

To whom correspondence should be addressed. E-mail: kvinod@iun.edu

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K. Vinodgopal and J. Peller

near future, making effective treatment process prior to discharge imperative. A

signi cant regulatory concern regarding any treatment process is the necessity to
identify any intermediates so that no toxic byproducts are generated during such
a process. Therefore, it is important that a comparison of the relative ef ciencies
of the AOPs mentioned above vis--vis this prototypical azo dye, Acid Orange 7
(AO7), include a clear identi cation of the intermediates generated and the extent
of mineralization achieved with each method.
Sonochemical degradation methods involve irradiating aqueous solutions containing the organic pollutant with ultrasound [4 9]. Propagation of an ultrasound wave
in aqueous solution leads to the formation of cavitation bubbles; a prerequisite for
these bubbles is the presence of a dissolved gas [10]. The collapse of these bubbles
spawns extreme conditions such as very high temperatures and pressures, which
in turn leads to the dissociation of H 2 O and the production of radical species such
as OH. , HOO. etc. In recent years, evidence has accumulated indicating that higher
ultrasound frequencies (at approx. 400 kHz) are more favorable for the production
of OH [8, 11]. Several recent studies have also focused on the aspect of understanding chemical reactivity of these radicals in a sonolytic reaction [12 16].
Radiolytically-generated radicals are also very effective in degrading organic
compounds [17 22]. Free radicals are also formed when water is irradiated with
ionizing radiation such as -rays or a high-energy electron beam. In the absence
of speci c scavengers, hydroxyl radicals (. OH) and hydrated electrons (e
aq ) are
the major reactive species produced in a neutral or alkaline aqueous solution. By
scavenging aqueous electrons with suitable scavengers such as N2 O one can induce
oxidative degradation of the organic substrates with . OH radicals.
While the commercial application of ionizing radiation to treat routine industrial
waste is still far from marketability, transient ionizing radiation methods such as
pulse radiolysis provide unique ways to deduce mechanisms of radical attack on
such organic substrates. We have utilized product identi cation and pulse radiolytic
methods as a tool to elucidate kinetics and reaction mechanism of the free radical
initiated oxidation processes. A systematic comparison of the sonochemical and
radiolytic degradation of the textile azo dye AO7 is presented in this paper. By
comparing the intermediates formed and decay mechanisms in the two different
methods of the mineralization of the azo dye AO7, we can hopefully provide new
insights into the development of new advanced oxidation processes for the treatment
of such industrial waste.
EXPERIMENTAL

AO7, also known as Orange II, was obtained from Aldrich and puri ed by
recrystallization and column chromatography as per details described elsewhere.
Steady-state -radiolysis was carried out in sealed vials at 296 K. The samples
vials were irradiated with a 60 Co source and each vial was withdrawn from the
core at different intervals. The dose rate as determined by Fricke dosimetry was

Radiolytic and sonolytic degradation of Acid Orange 7

309

88 Gy/ min. For pulse radiolysis experiments, irradiation was performed with
electron pulses (5 ns, approx. 1017 eV g1 pulse) from the Notre Dame 7-MeV
ARCO-LP-7 linear accelerator. Sonolysis experiments were carried out with a
640 kHz sonolysis setup (Ultrasonic Energy Systems, Panama City, FL, USA). A
specially designed glass vessel was attached to the transducer with silicon rubber.
Ultrasound irradiation of the solution was carried out with oxygen gas constantly
bubbling through the solution.
Samples of the dye solution at appropriate time intervals during the sonolysis, or
radiolysis experiments were taken out for analysis. The intermediates formed during
the degradation process were monitored using a HPLC (Waters Model 600 solvent
delivery system with a 996 Photodiode array). The mobile phase was an ammonium
phosphate buffer, which was maintained at 100% initially for 2 min and then
combined with methanol in a linear gradient from 0% to 100% methanol in 28 min.
Analysis of total oganic carbon (TOC) was carried out using a Shimadzu Model
500 TOC analyzer. As in the HPLC analyses, samples were taken out at appropriate
intervals for TOC analyses during all three degradation methods. Oxalate, formate
and other inorganic ions such as SO2
4 were determined by ion chromatography
using a Dionex model 500 DX ion chromatograph. It was equipped with a 20-cm
Ion Pac As12ASC column protected by a Ion Pac Ag12A guard column. The eluent
generally consisted of an aqueous solution containing a mixture of NaHCO3 and
Na2 CO 3 at concentrations of 0.3 mM and 2.7 mM, respectively. The ow rate of
the eluent was generally 1.5 ml/min. Identi cation of ionic products was achieved
with a conductivity detector and comparison with standards.

RESULTS AND DISCUSSION

Sonolysis
Acoustic cavitation is the single most step that in uences the sonochemical process.
The nonlinear acoustic process that is controlled by the nucleation, growth and
implosive collapse of bubbles produce enormous local temperatures (10 000 K) and
pressure (up to 10 000 atm). Under these extreme conditions the water molecule is
cleaved to form H. and . OH radical species.
H O ))))! H. C. OH
(1)
2

Transient radicals would then recombine or react with other chemical species
present in the medium. It has been shown that the reactivity of these radicals
is strongly dependent on the frequency of the sonolysis [8, 23, 24]. At high
frequencies, such as the one employed in the present experiments, the collapse of
the bubble occurs quickly. Thus, the probability of ejection of H. and . OH radicals
before they undergo recombination is signi cantly enhanced at higher frequency.
In the present experiments we have utilized the sonolytically produced . OH
radicals to react with the dye AO7. Sonolysis of the aqueous AO7 solution

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K. Vinodgopal and J. Peller

Figure 1. Absorption spectra of an AO7 solution (82 M) recorded at different time intervals
following sonolysis in oxygen-saturated solution at high frequency. The absorption spectra were
recorded at time intervals of (a) 0, (b) 15, (c) 30, (d) 90, (e) 180 and (f) 360 min.

(82 M) under oxygen-saturated conditions at 620 kHz leads to rapid decolorization as illustrated in Fig. 1 Hydroxybenzenesulfonic acid (HBS) was determined by HPLC analysis as the major reaction intermediate with trace amounts
of 1,2-naphthaquinone also being detected. In fact, by the rst 15 min, the AO7 as
well as the major intermediates had disappeared. While the HPLC gradient methods
that were employed indicated the complete disappearance of AO7, it also indicated
the buildup of a fast eluting component, which was most likely a low molecular
weight carboxylate anion, such as oxalate and/ or formate. The formation of such
low molecular weight acids is consistent with the decrease in pH that accompanies
the degradation of the dye. The pH of the aqueous dye solution changes from 4.3 to
2.9 following 6 h of sonication. In order to verify the nature of this nal product, we
have carried out ion chromatographic analysis. The IC enables us to unambiguously
identify the nal end product of sonication as oxalate and formate ions. Figure 2
shows the kinetics of the disappearance of AO7 along with the formation of HBS,
oxalate and formate ions.
It should be noted that in oxygenated solutions, sonication of water can lead
to the formation of hydroperoxy radicals and hydrogen peroxide as well. These
secondary radicals can initiate degradation of the dye substrate. The primary role of
OH radicals in the oxidative degradation of AO7 can be determined by employing
a . OH radical scavenger. When the sonolysis of AO7 was carried out in a aqueous
solution containing 2.5% t-butanol, the degradation of the dye was inhibited. Since
t-butanol is an excellent scavenger of hydroxide radicals, it preferentially competes
with AO7 for reacting with . OH radicals. It is therefore reasonable to conclude that
the initial step in the degradation mechanism is attack by the . OH radical on the dye
solute particle at or near the surface of the cavitation bubble.

Radiolytic and sonolytic degradation of Acid Orange 7

311

Figure 2. Kinetics of the sonochemical degradation of AO7 in an oxygen-saturated solution. Also

shown are the growth and decay curves of the intermediates HBS, oxalate and formate ions.

-Radiolysis
As discussed in the Introduction, -radiolysis of water produces a variety of radicals
which can react with the organic substrate present in the solution. The selectivity
of the reactive conditions can be improved by using appropriate scavengers. For
example, oxidizing conditions are achieved by saturating the solution with N2 O.
Hydrated electrons formed by the radiolysis of water are readily scavenged by N 2 O
to generate . OH radicals (reactions 3 and 4):
.
H2 O e!. OH, e
aq , H
.

e
aq C N2 O C H2 O ! N2 C OH C OH

(2)
(3)

Degradation of the dye is observed when N2 O-saturated aqueous solutions of the

AO7 was subjected to -radiolysis.
AO7 C. OH ! Products

(4)

The samples taken out at different time intervals were analyzed with HPLC. The
only identi able product formed as a result of . OH radical attack was once again
HBS. Figure 3 shows the decay trace of AO7 and the formation of HBS at the end
of radiolysis experiment.
We have also compared the extent of mineralization achieved in the two processes
by monitoring the total organic carbon (TOC) content of the solution. The decrease
in the TOC content of the dye solution with time for the two different AOPs is
plotted in Fig. 4. What is clear however in the sonochemical degradation is that
the residual TOC present after 6 h of sonication can be attributed to the oxalate and
formate ions present in solution.

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K. Vinodgopal and J. Peller

Figure 3. Kinetics of the radiolytic degradation of AO7 in an oxygen-saturatedsolution. Also shown

are the growth and decay curves of the intermediates HBS, oxalate and formate ions.

Figure 4. Plot of the degradation of AO7 by sonochemical and radiolytic methods monitored as a
function of the Total Organic Content (TOC) versus time.

Reaction pathways
There are a number of reports in literature on the oxidative degradation of AO7,
ranging from ozonation to biodegradation and noncatalytic oxidations. The intermediates and end products identi ed in all of these studies are quite similar. In the
cases of the photocatalytically induced OH radical initiated degradation of AO7,
Zepp et al. identify only HBS as an intermediate [25], whereas Ranganathan et al.
report the presence of both 1,2-naphthaquinone and HBS as intermediates during
the microbial oxidation of AO7 [26]. Given the structure of the AO7 it would be
reasonable to assume that the initial OH-AO7 radical adduct formed is centered on
the electron rich naphthalene ring. On the other hand, the detection of HBS as an
intermediate in all of the AOPs under discussion here, suggests that initial radical
attack could be occurring on the benzene moiety. However, the inability to detect
naphthaquinone as an intermediate could be due to rapid oxidation to end products

Radiolytic and sonolytic degradation of Acid Orange 7

313

Figure 5. Transient absorption spectra of the pulse radiolytically-generated OH radical adduct of

AO7. The spectrum was recorded at 13 (f) and 362 s (F) following the radiolysis of a N2 Osaturated solution of AO7 at pH 7.

and the lack of a substantial steady state concentration. To resolve the mechanism
of . OH radical-initiated attack, we have used pulse-radiolysis methods to further
probe the oxidation of AO7 in aqueous solution.
Time-resolved transient absorption spectra were recorded following the pulse
radiolysis of AO7 at pH 7 in N2 O saturated aqueous solutions in the absence and
presence of 0.1 M azide ion (Figs 5 and 6, respectively). In the absence of azide
radicals, the observed spectrum should be that of the . OH radical adduct. The . OH
radical adduct of AO7 produced during this radiolytic process exhibits characteristic
absorption peaks at 350 and 560 nm.
These pulse-radiolysis studies characterize the initial chemical events between the
. OH radical and AO7. The question then arises how this . OH radical adduct further
leads to the rupture of azo bond and, thus, initiates the oxidative degradation of the
dye. The decay of the transient absorbance following pulse radiolysis of the N2 O
saturated AO7 is quite slow. Therefore, we have examined the decay of the radical adducts at longer times. While the 350 nm absorption band remains unaffected
even at long time scales, the transient absorbance, centered at 550 nm decreases
after 360 s.
The transient spectrum generated by pulse radiolysis of N2 O-saturated AO7 in
the presence of azide ions is shown in Fig. 6. Azide ions scavenge hydroxide
radicals to produce azide radicals. These radiolytically generated azide radicals
can now participate in direct electron transfer with a substrate such as AO7, thereby
providing a convenient method for the generation of the cation radical of AO7 as
per equations (5) (7):
H2 O ! . OH C e
aq

.
.
N3 C OH ! N3 C OH
AO7 C . N 3 ! . AO7C C N
3

(5)
(6)
(7)

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K. Vinodgopal and J. Peller

Figure 6. Transient absorption spectra of the pulse radiolytically generated cation radical of AO7.
The spectrum was recorded at 13 s (f) and 362 s (F) following the radiolysis of a N2 O-saturated
solution of AO7 containing 0.1 M sodium azide.

The oxidation of the AO7 in the AOPs under discussion could proceed as in the
case of azide ions by direct electron transfer via the formation of the cation radical
of AO7 and its subsequent decay. While the transient spectra in Figs 5 and 6 show
identical absorption maxima at 350 nm, the broad absorbance at 550 nm seen for the
pure OH radical adduct in Fig. 5 is absent in Fig. 6 in the presence of azide radicals.
The transient spectrum in the presence of azide radicals remains the same even at
very long time scales, suggesting that the cation radical of the AO7 is quite stable
under the conditions of pulse radiolysis.
A variety of groups have studied the reaction of . OH radicals with azobenzene
[9, 27] and related azo dyes. They conclude that the addition of . OH radicals to
the azo double bond is the rst step in the sequence of reactions that leads to the
eventual oxidation of the substrate. In their transient studies on the reaction of
. OH radicals with azobenzene, Panjakar and Mohan have observed two primary
transients: one resulting from the attack of the . OH on the benzene ring with max
at 330 nm and the other transient arising from the attack on the azo bond with
max at 420 nm [27]. In the presence of the electron-rich naphthalene ring, the
initial . OH attack should not occur on the azo bond as suggested by these previous
authors. Comparison with earlier studies by Schuler et al. on p- uorophenol [28]
and 1-naphthol [29] strongly suggest that the transient at 550 nm observed in the
. OH radical adduct spectra can be attributed to the naphthaquinone . OH radical. The
pulse radiolysis studies therefore seem to suggest that initial radical attack occurs
on the naphthalene ring followed by formation of naphthaquinone and the rupture of
the orange chromophore. Although our HPLC methods identify HBS as the major
reaction intermediate with traces of 1,2-naphthaquinone, the pulse radiolysis studies
indicate that 1,2-naphthaquinone could be undergoing rapid oxidation to another
end product, thus denying the chance to observe this intermediate in concentrations
comparable to that of HBS.

Radiolytic and sonolytic degradation of Acid Orange 7

315

Figure 7. Reaction pathway for the hydroxide radical-induced degradation of AO7.

The similarity of the reaction pathway in the degradation approaches, viz.,

radiolysis and sonolysis is evident from the single identi able intermediate, HBS,
produced in the experiments discussed above. It should be noted that . OH radical
is the primary oxidizing species produced by the two AOPs. While the method of
production of the hydroxide radicals is different, the eventual initiation of oxidation
begins with them in each of these methods. It is reasonable to conclude that
oxidation of the dye starts with the formation of a hydroxyl radical adduct followed
by the formation of 1,2-naphthaquinone, the rupture of the azo bond leading to
the formation of HBS and eventually the breakup of the aromatic rings. The . OH
radical-mediated reaction pathway is summarized in the scheme shown in Fig. 7.
The results presented above show that hydroxyl radical mediated oxidation using
any of the AOPs discussed above is an effective method for degrading textile azo
dyes.
Acknowledgements
K. V. acknowledges the support of Indiana University Northwest through a Grant-inAid. K. V. also wishes to acknowledge NSF Grant CHE-9512052 for the purchase
of an HPLC and the Notre Dame Radiation Laboratory for use of their facilities.
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