Environmental Technology

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Integration of photocatalysis and biological

treatment for azo dye removal – application to
AR183

Derradji Chebli , Florence Fourcade , Stephan Brosillon , Saci Nacef &

Abdeltif Amrane

To cite this article: Derradji Chebli , Florence Fourcade , Stephan Brosillon , Saci Nacef
& Abdeltif Amrane (2011) Integration of photocatalysis and biological treatment for azo
dye removal – application to AR183, Environmental Technology, 32:5, 507-514, DOI:
10.1080/09593330.2010.504236

To link to this article: https://doi.org/10.1080/09593330.2010.504236

Published online: 03 May 2011.

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Environmental Technology
Vol. 32, No. 5, April 2011, 507–514

Integration of photocatalysis and biological treatment for azo dye removal – application
to AR183
Derradji Cheblia, Florence Fourcadeb,c, Stephan Brosillond, Saci Nacefa and Abdeltif Amraneb,c*
a
Département de Génie des Procédés, Faculté des Sciences de l’Ingénieur, Université Ferhat Abbas, 19000 Sétif, Algeria;
b
Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Avenue du Général Leclerc, CS 50837, 35708 Rennes
Cedex 7, France; cUniversité Européenne de Bretagne, 5 Boulevard Laënnec, 35000 Rennes, France; dUniversité de Montpellier
2, LGPEB CC05, 2 place Eugene Bataillon, 34095 Montpellier Cedex 5, France
(Received 31 December 2009; Accepted 22 June 2010 )
Taylor and Francis

10.1080/09593330.2010.504236

The feasibility of coupling photocatalysis with biological treatment to treat effluents containing azo dyes was
examined in this work. With this aim, the degradation of Acid Red 183 was investigated. The very low
biodegradability of AR183 was confirmed beforehand by measuring the biological oxygen demand (BOD 5).
Photocatalysis experiments were carried out in a closed-loop step photoreactor. The reactor walls were covered by
TiO2 catalyst coated on non-woven paper, and the effluent flowed over the photocatalyst as a thin falling film. The
removal of the dye was 82.7% after 4 h, and a quasi-complete decolorization (98.5%) was obtained for 10 h of
irradiation (initial concentration 100 mg L−1). The decrease in concentration followed pseudo-first-order kinetics,
with a constant k of 0.47 h−1. Mineralization and oxidation yields were 80% and 75%, respectively, after 10 h of
pretreatment. Therefore, even if target compound oxidation occurs (COD removal), indicating a modification to the
chemical structure, the concomitant high mineralization was not in favour of subsequent microbial growth. The
BOD5 measurement confirmed the non-biodegradability of the irradiated solution, which remained toxic since the
EC50 decreased from 35 to 3 mg L−1. The proposed integrated process appeared, therefore, to be not relevant for the
treatment of AR183. However, this result should be confirmed for other azo dyes.
Keywords: photocatalysis; azo dyes; kinetics; biodegradability; toxicity

Introduction non-destructive characteristic of these processes, their

Azo dyes are widely used in the textile industry, for
example in leather tanning in North Africa. This wide-
spread use results in the production of large amounts of
coloured wastewater. Because of the potential toxicity
of some dyes and their by-products, such as aromatic
amines [1–2], these effluents may cause environmental,
visual and chemical pollution. Removal of azo dyes is a
great challenge for the scientific community and a lot
of studies have been carried out on the degradation of
these compounds by means of physical, chemical or
biological processes [3].
During aerobic wastewater treatment, low degrada-
tion rates are recorded owing to the low biodegradabil-
ity of azo dyes; some dyes are toxic or recalcitrant for
microorganisms. A conventional biological treatment,
therefore, appears inappropriate to treat this class of
molecules [2,4].
Physical techniques can be used to remove such
biorecalcitrant pollutants [5–6]: adsorption, floccula-
tion, electro-flocculation, reverse osmosis, ultrafiltra-
tion and coagulation have been applied. Owing to the
main drawback is the need for regeneration, which often
consists in expensive and post-treatment processes.
Indeed, the pollutant is only transferred into another
phase [1,7–8].
Advanced oxidation processes (AOPs) have also
been tested for dye degradation. These are based on the
formation of hydroxyl radicals [9], which are easy to
produce, are non-selective and are very reactive. The
high reactivity of these species results in oxidation
of the dyes into CO2, H2O, and inorganic ions or
biodegradable compounds [10]. Advanced oxidation
processes can be separated into three categories [2]:
oxidations based on Fenton-type reactions (homoge-
neous catalysis); and processes based on the application
of ozone (ozone catalysis) and processes deriving from
heterogeneous photocatalysis.
The combination of Fenton’s reagent with UV-visible
irradiation (photo-Fenton system), mainly used for
removal of biorecalcitrant compounds [11–12], results
in a better efficiency of degradation owing to a contin-
uous regeneration of Fe2+ catalyst via photoreduction of

*Corresponding author. Email: abdeltif.amrane@univ-rennes1.fr

ISSN 0959-3330 print/ISSN 1479-487X online

© 2011 Taylor & Francis
DOI: 10.1080/09593330.2010.504236
http://www.informaworld.com
508 D. Chebli et al.

Fe3+ and generation of hydroxyl radicals with hydrogen
peroxide [13]. In photoelectro-Fenton techniques, hydro-
gen peroxide is electrochemically generated in acid solu-
tion by reduction of oxygen on various electrode
materials [14].
In photocatalytic processes, hydroxyl radicals are
generated by the illumination of a photocatalyst [9],
which is in most cases a TiO2 semiconductor [10,15–
17]. When experiments were carried out with suspen-
sions of photocatalyst [16–19], a separation of the
photocatalyst from the solution was necessary. To solve
this problem, the photocatalyst can be deposited on an
appropriate support [10,20].
coupling photocatalysis and biological treatment to treat
polluted azo dye effluents.
Materials and methods
Azo dye
The azo dye, AR183, was purchased from Sigma
Aldrich (Isle d’Abeau Chesnes, France) and used with-
out further purification owing to its high purity, above
99%. The molecular structure of the dye is given in
Figure 1. Purified water (Elix Millipore equipment) was
used to prepare the coloured solutions.
Figure 1. Chemical structure of AR 183.

Recently, in order to degrade recalcitrant

compounds and reduce operational costs, several stud- Materials for photocatalysis
ies recommend the integration of processes, more espe- Photocatalyst characteristics
cially the coupling of advanced oxidative processes
with a biological treatment [21–22]. The design of such The photocatalyst was PC-500 Titania from Millennium
a two-step system depends on the choice of the unit Inorganic Chemicals, (anatase >99%; specific surface
operations that complement each other, and can lead to area >320 m2 ng−1; crystallite average size: 5–10 nm;
a synergistic effect. Predicting the performance of this characteristics from Millenium, Inorganic Chemicals,
coupling requires knowledge of the chemical and Hunt Valley, MD, USA). The PC-500 Titania was
biological properties of the main by-products and their coated on non-woven paper (natural cellulose fibre, 2
degradation potential with respect to each process. The mm thick) using a binder. The binder was an aqueous
optimal irradiation time corresponds to a reduction in dispersion of colloidal SiO2. The cellulose fibre was
the toxicity and an increase in the biodegradability of coated with a mixture of TiO2 and SiO2 (particle size
the by-products. The ultimate aim is to reduce the over- 20–30 nm; TiO2/SiO2 mass ratio of 1) using a size press.
all impact of the process when treating such recalcitrant The TiO2 surface load was 25 g m−2 after washing. In
organic compounds. The literature dealing with the this study the combined cellulose fibres, TiO2 and SiO2
coupling of advanced oxidation and biological treat- will be referred to as the photocatalyst.
ment is mainly focused on the treatment of wastewater
containing pesticides, p-nitrotoluene orthosulphonic
Photoreactor and light source
acid and phthalate, etc. [21–28], whereas only little
basic engineering research has addressed the combina- The irradiation of azo dye AR183 solution was carried
tion of the two processes and the parameters that affect out in a closed-loop step photoreactor (Figure 2), which
the global removal efficiency of azo dyes in water. The consisted of several parts: a tank, a pump, a spillway at
involved advanced oxidation process constitutes a
pretreatment in order to increase the biodegradability of
an effluent containing recalcitrant azo dyes, to form
non-toxic by-products more easily metabolized by
microorganisms [20].
Photocatalysis was chosen as a pretreatment, with
TiO2 coated on cellulose fibre [29] to avoid a supple-
mentary step of photocatalyst filtration. In addition, if
the efficiency of this association (photocatalysis/biolog-
ical treatment) is shown for azo dye removal, the use of
a solid catalyst avoids the need for a continuous addi-
tion of reactants, as is the case in the photo-Fenton reac-
tion (H2O2 + Fe2+), for instance. The use of SiO2 as a
binder with TiO2 to coat the catalyst on the cellulosic
fibre involves a reduction in the specific area of TiO2.
The use of chemical vapour deposition or the sol–gel
method [30] does not present this drawback because the
TiO2 is chemically bonded with the support. The objec-
tive of this work was to consider the feasibility of Figure 1. Chemical structure of AR183.
 Environmental Technology 509

and filtered through a Millipore filter (Millex®-HV-0.45

µm) to avoid particles entering the analytical apparatus.
The initial pH of the solution was the natural pH of the
dye, i.e. 6.18.
Dissolved organic carbon (DOC) was measured by
means of a 1010 O.I. Analytical TOC analyser. Nitrate,
nitrite, chloride and sulphate anions were analysed by
means of a DIONEX DX120 ion chromatogram
equipped with a conductivity detector, using an AS9-
HC4 (25 × 8 mm ) column as the stationary phase, water
as the mobile phase and KOH as the eluent. The flow rate
was set at 1 mL min−1. Ammonium ions were analysed
by the Nessler method (NFT 90–015 standard [31]).
Chemical oxygen demand (COD) was measured by
means of a Test Nanocolor CSB 160 from Macherey-
Nagel (Düren, Germany).

BOD5 measurements
Measurement of BOD5 was carried out in Oxitop IS6
(from WTW, Alès, France) in order to check the non-
biodegradability of the azo dye.
Figure 2. Schematic view of the closed-loop step photore- The following procedure was applied to inoculate
actor: (a) photocatalytic media, (b) UV lamps (× 3), (c) tank,
(d) pump, (e) spillway. samples, the blank solution and the control solution:
100 g of soil was mixed in distilled water; after agitation
the solution was left to stand for 10 minutes; 20 mL of
the top and steps. The reactor was made of six regular supernatant was then harvested and mixed to distilled
steps of the same dimensions (depth/height/width: water to obtain a total volume of 2 L.
6 cm/6 cm/25 cm) covered with the photocatalyst The following mineral basis was used for all exper-
(0.18 m2; 72 cm × 25 cm corresponding to 4 g of TiO2). iments (g L−1): MmgSO4·7H2O, 22.5; CaCl2, 27.5;
Three UV lamps, Phillips PL-L24W/10/4P (λmax = FeCl3, 0.15; NH4Cl, 2.0; Na2HPO4, 6.80; KH2PO4, 2.80.
365 nm), were placed inside a cover. The radiant flux The BOD5 value was initially estimated based on
received by the solution was measured by means of a the COD value experimentally measured or calculated:
chemical actinometer (potassium ferrioxalate). The BOD5 = COD/1.46. The range of expected BOD5
actinometer was irradiated under similar conditions as measurement was then deduced and hence led to the
those considered during the degradation studies. The volumes of sample, ground solution and nitrification
incident photon flux, P0, was measured at (38 ± 0.2) inhibitor (10 mg L−l solution of N-allylthiourea) that
W m−2. have to be added to the shake flask of the Oxitop
Schematic view of the closed-loop step photoreactor: (a) photocatalytic media, (b) UV lamps ( × 3), (c) tank, (d) pump, (e) spillway.

In a typical experiment, 3 L of pesticide solution of

Figure 2.

apparatus.
varying concentration were introduced into the system. A similar protocol was applied for the control
The solution was pumped into the tank at a flow rate of sample except that it was replaced by a solution of
120 L h−1. Samples were periodically withdrawn from easily biodegradable compounds, namely glutamic acid
the tank to evaluate the remaining concentration of the (150 mg L−1) and glucose (150 mg L−1). Before use,
target compound. The liquid flow on the photocatalyst KOH was added to achieve neutral pH (7.0 ± 0.2). A
was a thin falling film with a thickness of about 1 mm. similar protocol was also considered for the blank solu-
After adsorption equilibrium was reached in the dark tion, for which the sample was replaced by water so as
(30 min), the UV light was turned on to irradiate the to have a negligible BOD5 value.
solution and the first sample was taken (t = 0). The
evaporation was estimated each hour, and distilled
water was added to balance losses.
Toxicity
Toxicity was measured by means of the Microtox test
Analyses (Microtox 500 analyser), which is based on the inhibi-
In a typical photocatalysis experiment, at scheduled tory effect on a marine bacterial strain, Vibrio fischeri
times, 25 mL of samples were taken from the reactor NRRL B-11177 (standard ISO 11348-3 [32]).
510 D. Chebli et al.

Results and discussion production of ammonium ions corresponded approxi-

The degradation of Acid Red 183 in an aqueous solution mately to 12.5% of the initial nitrogen contained in
by photolysis (without TiO2), showed negligible degra- the target compound. The nitrate ion concentration
dation of AR183, if compared with the values recorded followed a similar trend to the ammonium ions, but a
during photocatalysis. The decrease in the azo-dye lower final level was recorded (1.4% of the nitrogen
concentration in the presence of TiO2 was therefore only contained in AR183). The concomitant increases in
due to the heterogeneous photocatalytic degradation. nitrates and ammonium (Figure 5) indicated that
During photocatalysis, the degradation yield after nitrates did not only result from ammonium oxidation
4 h of irradiation time was 82.7% and quasi-complete but were also produced directly from the intermediate
decay (98.5%) was achieved for an irradiation time of organic by-products, which could contain nitriso, nitro,
10 h (Figure 3). It should be noted that only 7.8% of azo N-hydroxy organic functions, as suggested by Guillard
dye was adsorbed on the photocatalyst after 30 min et al. [33]. It is well known that NH4+ ions are slowly
adsorption equilibrium time (data not shown). transformed into NO3− by photocatalysis. The detection
Time-course of the photocatalytic degradation of AR183 as measured by the ratio C/C 0 (▲) and mineralization as measured by the ratio DOC/DOC 0 (•) during the photocatalytic degradation of AR183 azo dye for an initial concentration of 100 mg L −1 in the closed-loop step reactor.

The decrease in the concentration followed a

Figure 3.
of nitrite traces was consistent with nitrogen oxidation
pseudo-first-order kinetic with the value of the to nitrates (data not shown). At the end of the irradiation
constant k being 0.47 h−1. High degradation rates were time, the inorganic nitrogen balance did not reach
recorded during the first two hours (52.7% of degrada- stoichiometry, since only 13.9% of the initial amount of
tion after 1.5 h of irradiation). This was in agreement nitrogen could be accounted for. The lack of nitrogen
with the readily photocatalytic degradation of the visi- stoichiometry may be explained by the formation of
ble chromophore of the initial molecule, as shown nitrogen gas (N2 not monitored in this study). The
from the evolution of the visible spectra with time release of chloride ions (Figure 6) was followed during
(Figure 4). the photocatalysis of AR183 solution. At the end of the
The formation of inorganic ions (NO2−, NO3−, NH4+, irradiation time, the chlorine balance reached stoichi-
Figure 4. Evolution of the UV-visible spectrum during the photocatalytic degradation of AR183.

− ometry. This result confirms that the C–Cl bond is

Cl ) was monitored throughout the irradiation of Acid
Red 183 solution. The time-courses of the concentration easily broken and that the chlorine atom in the dye is
of nitrate and ammonium ions are shown in Figure 5. one of the first hetero-atoms attacked during a photocat-
After 6 h of irradiation, the concentration of ammonium alytic reaction, similar to the photocatalysis of pesticide
and nitrate ions reached a plateau (Figure 5). The total solutions [29,34].
Figure 5. Time-courses of NO 3− (▲) and NH4+ (•) concentrations during the photocatalytic degradation of AR183.

Figure 3. Time-course of the photocatalytic degradation of AR183 as measured by the ratio C/C 0 (▲) and mineralization as
measured by the ratio DOC/DOC0 (●) during the photocatalytic degradation of AR183 azo dye for an initial concentration of
100 mg L−1 in the closed-loop step reactor.
 Environmental Technology 511

Figure 4. Evolution of the UV-visible spectrum during the photocatalytic degradation of AR183.

Figure 5. Time-courses of NO3− (▲) and NH4+ (●) concentrations during the photocatalytic degradation of AR183.

As for inorganic nitrogen, the sulphur balance did well as the adsorption of sulphate ions on the catalyst
not reach stoichiometry; only 37% of the amount of [35].
Time-courses of SO 42− (▲) and Cl− (•) concentrations during the photocatalytic degradation of AR183.

sulphur was released as sulphate ions after 10 h of The mineralization of the solution was deduced by
Figure 6.

irradiation (Figure 6). At this time, a high mineraliza-
tion level was achieved (80%), showing that the
observed unbalance cannot be accounted for by the
presence of sulphur-containing intermediate by-prod-
ucts. It is possible that formation of SO2 occurred, as
monitoring the DOC removal, whereas the oxidation of
the target compound and its by-products was deduced
from COD removal (Figure 7). A low rate of DOC
decrease was recorded, and the final mineralization
level was 80% after 10 h of photocatalytic degradation
512 D. Chebli et al.

Figure 6. Time-courses of SO42− (▲) and Cl− (●) concentrations during the photocatalytic degradation of AR183.

Figure 7. Time-courses of the chemical oxygen demand (▲) and dissolved organic carbon (●) concentrations during photocat-
alytic degradation of AR183.

of AR183. Up until 3 h of irradiation, the decrease in accumulation of intermediates that are more resistant
COD was rapid, reaching 50% of removal; then, and than the target compound to further oxidation [36].
Time-courses of the chemical oxygen demand ( ▲) and dissolved organic carbon (•) concentrations during photocatalytic degradation of AR183.

until the end of the experiment, a low rate of COD In the context of the integration of a photocatalytic
Figure 7.

removal was recorded. This can be explained by the process with a biological treatment, the evolution of
 Environmental Technology
these global parameters has to be examined. A decrease
in COD involves an oxidation of the target compound
and, thus, a change in this chemical structure, and hence
can lead to a decrease in the toxicity of the target
compound and its by-products. On the other hand, the
mineralization should be limited, to ensure sufficient
residual organic carbon for a significant microbial
culture, since the objective is the use of by-products of
photocatalysis as substrates for microorganism growth.
From this, the favourable trend could be a decrease in
the ratio COD/DOC during the photocatalytic degrada-
tion of the target compound [21]. Moreover, the
concentration of the azo dye has to be the lowest possi-
ble, since previous studies in the laboratory highlighted
the non-biodegradability of this molecule.
In the case of AR183, the COD to DOC ratio
remained constant (COD/DOC = 3.3) throughout the
irradiation. Moreover, the remaining DOC amount was
very low for a total AR183 degradation, showing very
close kinetics of decolorization and mineralization.
Hence, the proposed integrated process for the degrada-
tion of AR183 azo dye did not seem to be appropriate.
Supplementary studies were therefore carried out on
the biodegradability of the solution from photocatalysis
experiments. The BOD was measured on the irradiated
solution (10 h) and showed a ratio of BOD5 to COD that
was less than 0.4, which confirmed the non-biodegrad-
ability of the irradiated solution. Moreover, results from
the Microtox test clearly showed that during the
pretreatment the toxicity of the solution increased, since
the EC50 (the effective concentration at which 50% of
the light is lost as a result of compound toxicity)
decreased from 35 mg L−1 to 3 mg L−1 after 10 h of irra-
diation. After photocatalysis, the solution was therefore
not only recalcitrant but also toxic for microorganisms.
The increase in the toxicity could be explained by the
presence of chromium (Cr(III)) associated with
the molecule of AR183 in the formulation provided by
the furnisher. During photocatalysis, oxidation of
Cr(III) into Cr(VI) could take place, leading to a higher
toxicity of the final solution.
Conclusion
Photocatalysis of a 100 mg L−1 solution containing
AR183 showed that 98.5% of the azo dye was removed
after 10 h of irradiation. In the same time, a mineraliza-
tion of 80% and a COD removal of 75% were obtained.
On the one hand, the decrease in the COD showed
an oxidation of the target compound and then a change
in the chemical structure; a better biodegradability or
less toxicity was then expected. However, on the other
hand, the high decrease in the DOC, characteristic of a
high mineralization yield after irradiation, did not
allow significant microbial growth. Moreover, BOD5
513
and toxicity measurements clearly showed the non-
biodegradability and the high toxicity of the solution
after photocatalysis. The formation of chromium (VI)
during pretreatment could explain the increase in the
toxicity; but this assumption should be subsequently
confirmed.
Similar work on other azo dyes is needed to reach
any conclusions about the efficiency and the relevance
of the proposed integrated process that couples photoca-
talysis with biological treatment.
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